Uses of α-oxy(oxo) sulfides and ethers in foodstuffs and flavors for foodstuffs

ABSTRACT

Processes and compositions are described for use in foodstuff flavors and as foodstuff article aroma and taste augmenting and enhancing materials of at least one α-oxy(oxo) sulfide and ether having the structure: ##STR1## wherein X is one of: ##STR2## Z is one of sulfur or oxygen; when R 1  and R 2  are taken separately, R 1  is hydrogen or methyl, and R 2  is methyl; and when R 1  and R 2  are taken together, R 1  and R 2  form phenyl moieties; and Y is one of C 1  -C 4  alkyl, C 3  or C 4  alkenyl, acetyl, methoxycarbonylmethyl, or 1,3 -diethylacetonyl. The compounds of our invention are useful in augmenting or enhancing the flavor and aroma nuances of berry flavors, cereal-like flavors, nut flavors, broccoli flavors, onion flavors, citrus flavors (including neroli, bergamot, lime), jasmin flavors, grapefruit flavors, concord grape flavors, blackcurrant flavors, milk caramel flavors (e.g., dulce de leche-like flavors), vegetable flavors, cucumber flavors, celery flavors and spice flavors.

This application is a divisional of application for U.S. Pat. Ser. No.730,537, filed on Oct. 7, 1976.

BACKGROUND OF THE INVENTION

The present invention relates to α-oxy(oxo) sulfides and ethers andnovel compositions using such compounds to augment or enhance the flavorand/or aroma of foodstuffs.

There has been considerable work performed related to substances to (orin) various consumable materials including foodstuffs. These substancesare used to diminish the use of natural materials, some of which may bein short supply and to provide more uniform properties in the finishedproduct. The following flavor and aroma notes are desirable,particularly in berry fruit flavored foodstuffs, vegetable flavoredfoodstuffs, spicey foodstuffs and citrus fruit flavored foodstuffs:

Aroma

Green/spicey,

Sweet,

Fruity,

Fresh/fruity,

Gooseberry-like,

Concord grape-like,

Grape-like,

Almond-like,

Nutty,

Cereal-like,

Lachrymatory onion-like,

Oniony,

Green onion-like,

Leek-like,

Broccoli-like,

Grapefruit-like,

Celery stalk-like,

Floral,

Rosey,

Woody,

Blackcurrant-like,

Buchu leaf oil-like,

Citronellal-like,

Neroli-like,

Bergamot-like,

Violet leaves-like,

Jasmin-like,

Melon-like,

Cucumber-like,

Green,

Vegetable,

Sweet/floral.

Flavor

Spicey,

Sweet,

Fruity,

Milk caramel-like (dulce de leche-like),

Gooseberry-like,

Broccoli-like,

Nutty,

Cereal-like,

Oniony,

Grape-like,

Concord grape-like,

Citrusy,

Grapefruit-like,

Green fruit-like,

Mandarin-like,

Petitgrain-like,

Blackcurrant-like,

Minty,

Astringent,

Coriander-like,

Green,

Piney,

Citronellal-like,

Violet leaves-like,

Melon-like,

Cucumber-like,

Green,

Floral

Floral/green

Vegetable,

Garlic-like.

Prior to this last decade it was the general opinion among those skilledin the art that compounds containing the mercapto or -SH moiety orsubstituted mercapto or -SR moiety (where R is an organic group such asalkyl or acetyl) were desirable for use in conjunction with foodstuffflavors only where alliaceous flavors were concerned, or where meatyflavors were concerned or where coffee-type flavors were concerned, andwere not desirable for use in conjunction with other more delicate typeflavors, e.g., blackcurrant, citrus and vegetable. However, within thelast decade certain mercapto compounds have been ascertained to beuseful, for example, in blackcurrant and buchu leaf oil-like flavors. Inaddition, within the last decade such compounds have been ascertained tobe highly useful in perfumery also.

Thus, for example, British Pat. Nos. 1,423,914 and 1,423,915 issued onFeb. 4, 1976, teach that certain mercapto derivatives which arealiphatic or cycloaliphatic compounds having the formula: ##STR3##wherein X¹ represents a hydroxyl group or an acyl-oxy group, and X²represents a hydrogen atom; R¹, R², R³ and R⁴ may be the same ordifferent and each represents a hydrogen atom or a univalent aliphatichydrocarbyl group; or R¹ and R³ or R⁴, together with the interveningcarbon atoms, constitute a cycloaliphatic ring, are useful as perfumingagents as exemplified by adding 3-methylthio-hexanol to a perfume basecomposition of the "Fleuri" type wherein the 3-methylthio-hexanol issaid to give rise to a green, fruity aroma reminiscent of that ofrhubarb.

Furthermore, for example, Canadian Pat. No. 983,050 issued on Feb. 3,1976, teaches that 3,7-dimethyl-octa-2,6-dienyl-mercaptan (thiogeraniol)of the formula: ##STR4## is used in making up a "synthetic buchu leafoil" and imparts to a lavender type composition a greener and moreherbal fragrance. USSR Pat. No. 345,677 teaches thatpara-menthane-8-thiol-3-one is useful as a synthetic black currantflavoring for foodstuffs. This compound has the structure: ##STR5##German Offenlegungschrift Pat. No. 2,316,456, published on Oct. 11, 1973discloses the use of certain thio alcohols or their corresponding estersin perfumery and in perfumed articles, such as detergents, cosmetics andwaxes. Such mercapto alcohols having the generic structure: wherein R₁is a hydrocarbon moiety having from 1 up to 7 carbon atoms and R₂ is oneof hydrogen, methyl or ethyl.

U.S. Pat. Nos. 3,950,429 issued on Apr. 13, 1976, and 3,952,062 issuedon Apr. 20, 1976, disclose certain alkylthiosubstituted oxo-terpenoidshaving 10 carbon atoms in the terpenoid skeleton as useful in perfumeryand in flavors, particularly for providing vegetable notes. The genericstructure of the compounds is as follows: ##STR6## wherein R¹ representshydrogen or together with R⁴ represents a C -- C bond,

R² represents hydrogen or together with R⁶ represents adimethylmethylene group, or, when R⁶ is isopropyl, together with R⁵represents a C -- C bond,

R³ represents hydrogen or together with R⁶ represents adimethylmethylene group,

R⁴ represents hydrogen or together with R¹ represents a C -- C bond,

R⁵ represents hydrogen or, when R⁶ signifies isopropyl, together with R²represents a C -- C bond,

R⁶ represents isopropyl or together with R² or with R³ represents adimethylmethylene group,

R⁷ represents methyl,

X represents a C -- C double bond taking the place of a C -- C singlebond,

m = 0 to 2,

Y represents oxo bound to a primary or secondary C-atom and Z representsmercapto or lower alkylthio located in the β-position to the carbonylfunction,

provided that when R², R³ and R⁵ represent hydrogen, R⁶ representsisopropyl, R⁴ together with R¹ represents a C -- C bond, Y is β to thecarbon atom bearing the substituent R⁷, m = o, Z is α to the carbon atombearing the substituent R⁵ and β to the carbon atom bearing thesubstituent R³, then Z represents alkylthio.

However, none of the disclosure of the prior art contains a teaching tothe effect that compounds having the generic structure: ##STR7## whereinX is one of: ##STR8## Z is one of sulfur or oxygen; when R₁ and R₂ aretaken separately, R₁ is hydrogen or methyl, and R₂ is methyl; and whenR₁ and R₂ are taken together, R₁ and R₂ form phenyl moieties; and Y isone of C₁ -C₄ alkyl, C₃ or C₄ alkenyl, acetyl, methoxycarbonylmethyl, or1,3-diethylacetonyl have the ability to create the following aroma andflavor notes in foodstuffs:

Aroma

Green/spicey,

Sweet,

Fruity,

Fresh/fruity,

Gooseberry-like,

Concord grape-like,

Grape-like,

Almond-like,

Nutty,

Cereal-like,

Lachrymatory onion-like,

Oniony,

Green onion-like,

Leek-like,

Broccoli-like,

Grapefruit-like,

Celery stalk-like,

Floral,

Rosey,

Woody,

Blackcurrant-like,

Buchu leaf oil-like,

Citronellal-like,

Neroli-like,

Bergamot-like,

Violet leaves-like,

Jasmin-like,

Melon-like,

Cucumber-like,

Green,

Vegetable,

Sweet/floral.

Flavor

Spicey,

Sweet,

Fruity,

Milk caramel-like (dulce de leche-like),

Gooseberry-like,

Broccoli-like,

Nutty,

Cereal-like,

Oniony,

Grape-like,

Concord grape-like,

Citrusy,

Grapefruit-like,

Green fruit-like,

Mandarin-like,

Petitgrain-like,

Blackcurrant-like,

Minty,

Astringent,

Coriander-like,

Green,

Piney,

Citronellal-like,

Violet leaves-like,

Melon-like,

Cucumber-like,

Green,

Floral,

Floral/green,

Vegetable,

Garlic-like.

Furthermore, other substituted mercaptans in the prior art which areshown to be useful in perfumery are indicated to have rhubarb-like, orberry, or other floral-type fragrances, e.g., ionone and ironederivatives having the structure: ##STR9##

Furthermore, certain α-mercaptoketones are disclosed in the prior art,but only in meat flavors. Thus, U.S. Pat. No. 3,773,524 issued on Nov.20, 1973, discloses the use of α-ketothiols of the formula: ##STR10##wherein R₁ is methyl or ethyl; and R₂ and R₃ are hydrogen, methyl orethyl to alter the meat flavor and aroma of foodstuffs. U.S. Pat. No.3,892,878, issued on July 1, 1975, discloses the use of certainhydroxymercaptoalkanes to alter the flavor of foodstuffs, for example,2-mercapto-3-butanol used in meat flavors. The genus disclosed by U.S.No. 3,892,878 is as follows: ##STR11## wherein X is oxygen or sulfur, nis 0 or 1 R₁ -R₇ are the same or different and each is hydrogen or loweralkyl of 1-4 carbon atoms, a and b are the same or different and eachrepresents an integer of from 0 to 10 when n is 0 and when n is 1, a andb are the same or different and each represents an integer of from 1 to10. 3-mercaptoheptanon-4 is disclosed per se in U.S. Pat. No. 2,888,487,issued on May 26, 1959. 3-mercapto-2,6-dimethyl-heptan-4-one isdisclosed in Chem. Abstracts 6478 (d) Vol. 62, 1965 (abstract ofAsinger, Diem and Schaefer, Monatsh. Chem. 95 (4-5), 1335-54 (1964).Beilstein E-IV-1 discloses 2-mercapto-2,4-dimethyl-pentan-3-on page4039, 1-mercapto-octan-2-on at page 4040; and 1-mercapto-nonan-2-on at4052 and 1-mercapto-undecan-2-on at page 4,060.

U.S. Pat. No. 3,922,366 issued on Nov. 25, 1975, discloses theenhancement of foodstuffs by addition of a small but effective flavormodifying amount of a compound of the general formula: ##STR12## whereinR₁ is hydrogen or alkyl and R₂ is alkyl or furfuryl. The flavor nuanceswhich are enhanced or altered are those which are found in coffeeflavors and aromas.

THE INVENTION

The invention comprises novel compositions, and foodstuffs containingα-oxy(oxo) sulfides and ethers having the structure: ##STR13## wherein Xis one of: ##STR14## Z is one of sulfur or oxygen; when R₁ and R₂ aretaken separately, R₁ is hydrogen or methyl, and R₂ is methyl; and whenR₁ and R₂ are taken together, R₁ and R₂ form phenyl moieties; and Y isone of C₁ -C₄ alkyl, C₃ or C₄ alkenyl, acetyl, methoxycarbonylmethyl, or1,3-diethylacetonyl the specific embodiments of which are describedhereinafter by way of example and in accordance with which it is nowpreferred to practice the invention.

Such α-oxy(oxo) sulfides and ethers are obtained by reacting an alkanonewith SO₂ Cl₂ to form an α-chloroalkanone; reacting the α-chloro-alkanonewith either an alkali metal mercaptide or an alkali metal alkoxide(depending on whether z is sulfur or oxygen) to form either an α-oxosulfide or an α-oxo ether which can be used for its food flavorproperties; or, if desired, reacting the resulting α-oxo sulfide orα-oxo ether with a reducing agent such as an alkali metal borohydride inorder to obtain an α-oxy sulfide or an α-oxy ether. Thus, theaforementioned reaction sequence is illustrated as follows: ##STR15##wherein X is one of: ##STR16## Z is one of sulfur or oxygen; when R₁ andR₂ are taken separately, R₁ is hydrogen or methyl, and R₂ is methyl; andwhen R₁ and R₂ are taken together, R₁ and R₂ form phenyl moieties; and Yis one of C₁ -C₄, alkyl, C₃ or C₄ alkenyl, acetyl,methoxycarbonylmethyl, or 1,3-diethylacetonyl.

The reaction between the SO₂ Cl₂ and the ketone preferably takes placein the absence of a solvent at a temperature of between 15° C. and 40°C. The SO₂ Cl₂ is preferably added to the ketone. At the end of thereaction, the reaction mass is worked up, the chlorinated ketone beingdistilled in vacuo.

The resulting chlorinated ketone is then reacted with either an alkalimetal mercaptide or an alkali metal alkoxide. Preferably the alkalimetal mercaptide is sodium mercaptide, preferably which is prepared byreaction of sodium methylate with an appropriate mercaptan in methanol.Preferably the alkali metal alkoxide is sodium methoxide. Thechlorinated ketone is preferably contained in an inert solvent, e.g., inmethanolic solution. Preferably the methanolic solution of chlorinatedketone is slowly added to the pre-prepared alkali metal mercaptide oralkali metal alkoxide at a temperature of between 0° C. and 30° C.,preferably between 15° C and 30° C. The reaction mass is then extractedwith a solvent such as methylene chloride, and the resulting extract isthen worked up using evaporation and distillation, techniques or GLCtrapping whereby the α-oxo sulfide or α-oxo ether (as the case may be)is recovered. The resulting α-oxo sulfide or ether is then used ("asis") for its flavor properties; or it may be further reacted with areducing agent such as an alkali metal borohydride, conveniently sodiumborohydride. The reaction with sodium borohydride takes place in aninert solvent such as anhydrous ethanol at a temperature of between 20°C and 35° C. A solution in anhydrous ethanol of the α-oxo sulfide orether is added to a solution in anhydrous ethanol of the alkali metalborohydride. The reaction is carried out over a period of time ofbetween two and ten hours. At the end of the reaction, the reaction massis concentrated and is then admixed with water. The resulting mixture isthen acidified to a pH of between 2 and 3 and then extracted with aninert extraction solvent such as methylene chloride. The methylenechloride extract is then dried, evaporated, and the resulting α-oxysulfide or ether is distilled in vacuo or isolated by GLC trapping.

Alternatively, the α-chloro ketone may be reacted with an alkali metalhydrosulfide such as sodium hydrosulfide or an alkali metal hydroxidesuch as a sodium hydroxide to form the corresponding α-mercapto ketoneor α-hydroxy ketone. The α-mercapto ketone or α-hydroxy ketone may thenbe reacted with base (e.g., sodium methoxide) to form the alkali metalsalt. The alkali metal salt of the α-mercapto ketone or α-hydroxy ketoneis then reacted with an alkyl or alkenal halide (e.g., methallylchloride) thereby forming the desired α- oxo sulfide or α-oxo etherwhich may then, if desired, be used as such for its organolepticproperties, or it can be reduced with an alkali metal borohydride (e.g.,sodium borohydride) to the corresponding α-oxy sulfide or α-oxy ether.This reaction sequence is illustrated as follows: ##STR17## Specificexamples of α-oxy(oxo) sulfides and ethers produced using theafore-mentioned processes and their food flavor properties are asfollows (as set forth in Table I below:

                                      TABLE I                                     __________________________________________________________________________    COMPOUND       STRUCTURE          FLAVOR PROPERTY                             __________________________________________________________________________    3-methylthio-4- heptanone                                                                                        ##STR18##                                  __________________________________________________________________________    3-propylthio-4- heptanol                                                                      ##STR19##                                                                                        ##STR20##                                  __________________________________________________________________________    3-isobutylthio-4- heptanone                                                                   ##STR21##                                                                                        ##STR22##                                  __________________________________________________________________________    3-propylthio-4- heptanone                                                                     ##STR23##         Sweet, floral, jasmin and berry-like                                          aroma characteristic with sweet/floral                                        jasmin, grapefruit and black- currant                                         flavor character- istic at 2                __________________________________________________________________________                                      ppm.                                        3-(methallylthio)-2,6- dimethyl-4-heptanone                                                   ##STR24##                                                                                        ##STR25##                                  __________________________________________________________________________    3-crotylthio-2,6- dimethyl-4- heptanone                                                       ##STR26##         Floral, citronellal-like citrus,                                              grapefruit, woody aroma character-                                            istic and a citrus, grapefruit,                                               coriander- like flavor character- istic                                       at 3 ppm.                                   __________________________________________________________________________    3-allylthio-2,6- dimethyl-4- heptone                                                          ##STR27##                                                                                        ##STR28##                                  __________________________________________________________________________    3[(methoxycarbonyl)-  methylthio]-4- heptanone                                                ##STR29##         At 10 ppm, a sweet, sulfury, nutty,                                           meaty, cereal aroma character and a                                           sweet, meaty, nutty, cereal flavor                                            characteristic with an outstanding                                            mouthfeel effect.                           __________________________________________________________________________    3-methoxy-4-heptanone                                                                         ##STR30##         At 3 ppm, a sweet, fruity, gooseberry-li                                      ke, grape, almond aroma character with                                        a sweet, fruity, gooseberry-like,                                             nutty, grape flavor character.              __________________________________________________________________________    1-propylthio-1,3- diphenyl-2- propanone                                                       ##STR31##         At 0.5 ppm, a green onion aroma with a                                        lachrymating onion and biting effect                                          and a sweet, rubbery, meaty flavor                                            character- istic; at 2 ppm the garlic                                         aroma dominates along with the fresh                                          onion notes.                                __________________________________________________________________________    (1,3-diethylacetonyl) (1,3-diisopropylacetonyl) sulfide                                       ##STR32##         At 10 ppm, a grapefruit, floral and                                           woody aroma character with a sweet,                                           sulfury, grapefruit-like, mandarin                                            flavor character- istic and bitter                                            nuances.                                    __________________________________________________________________________    3-acetylthio-4- heptanone                                                                     ##STR33##         At 1 ppm a fresh fruity, blackcurrant-li                                      ke, buchu leaf oil-like, aroma with                                           meaty and sulfury nuances and a fresh                                         fruit, black- currant-like flavor                                             characteristic with an oniony                                                 aftertaste.                                 __________________________________________________________________________

When the α-oxy(oxo) sulfide and ether compound or compounds of ourinvention are used as food flavor adjuvants, or are used to augment orenhance the flavor or aroma characteristics of foodstuffs, the nature ofthe co-ingredients included with the said α-oxy(oxo) sulfides and ethersin formulating the product composition will also serve to augment theorganoleptic characteristics of the ultimate foodstuff treatedtherewith.

As used herein in regard to flavors, the term "augment" in its variousforms means "supplying or imparting flavor character or note tootherwise bland, relatively tasteless substances or augmenting theexisting flavor characteristic where a natural flavor is deficient insome regard or supplementing the existing flavor impression to modifyits quality, character or taste."

As used herein in regard to food flavors, the term "enhance" is usedherein to mean the intensification of a flavor or aroma characteristicor note without the modification of the quality thereof. Thus,"enhancement" of a flavor or aroma means that the enhancement agent doesnot add any additional flavor note.

As used herein the term "foodstuff" includes both solids and liquids,and ingestible materials or chewable but non-ingestible materials suchas chewing gum. Such materials usually do, but need not, havenutritional value. Thus, foodstuffs include soups, convenience foods,beverages, gelatin desserts, dairy products, candies, vegetables,cereals, soft drinks, snacks and the like.

Substances suitable for use herein as co-ingredients or flavoringadjuvants are well known in the art for such use, being extensivelydescribed in the relevant literature. Apart from the requirements thatany such materials be organoleptically compatible with theα-oxo-substituted chalcogenalkanes, non-reactive with theα-oxo-substituted chalcogenalkanes of our invention and "ingestibly"acceptable and thus non-toxic or otherwise non-deleterious, nothingparticularly critical resides in the selection thereof. Accordingly,such materials which may in general be characterized as flavoringadjuvants or vehicles comprise broadly stabilizers, thickeners, surfaceactive agents, conditioners, other flavorants and flavor intensifiers.

Stabilizer compounds include preservatives, e.g., sodium chloride;antioxidants, e.g., calcium and sodium ascorbate, ascorbic acid,butylated hydroxyanisole (mixture of 2- and3-tertiary-butyl-4-hydroxyanisole), butylated hydroxy toluene(2,6-di-tertiary-butyl-4-methyl phenol), propyl gallate and the like andsequestrants, e.g., citric acid.

Thickener compounds include carriers, binders, protective colloids,suspending agents, emulsifiers and the like, e.g., agar agar,carrageenan; cellulose and cellulose derivatives such as carboxymethylcellulose and methyl cellulose; natural and synthetic gums such as gumarabic, gum tragacanth; gelatin, proteinaceous materials; lipids;carbohydrates; starches, pectins and emulsifiers, e.g., mono- anddiglycerides of fatty acids, skim milk powder, hexoses, pentoses,disaccharides, e.g., sucrose corn syrup and the like.

Surface active agents include emulsifying agents, e.g., fatty acids suchas capric acid, caprylic acid, palmitic acid, myristic acid and thelike, mono-and diglycerides of fatty acids, lecithin, defoaming andflavor-dispersing agents such as sorbitan monostearate, potassiumstearate, hydrogenated tallow alcohol and the like.

Conditioners include compounds such as bleaching and maturing agents,e.g., benzoyl peroxide, calcium peroxide, hydrogen peroxide and thelike; starch modifers such as peracetic acid, sodium chlorite, sodiumhypochlorite, propylene oxide, succinic anhydride and the like, buffersand neutralizing agents, e.g., sodium acetate, ammonium bicarbonate,ammonium phosphate, citric acid, lactic acid, vinegar and the like;colorants, e.g., carminic acid, cochineal, tumeric, curcumin and thelike; firming agents such as aluminum sodium sulfate, calcium chlorideand calcium gluconate; texturizers, anti-caking agents, e.g., aluminumcalcium sulfate and tribasic calcium phosphate; enzymes; yeast foods,e.g., calcium lactate and calcium sulfate; nutrient supplements, e.g.,iron salts such as ferric phosphate, ferrous gluconate and the like,riboflavin, vitamins, zinc sources such as zinc chloride, zinc sulfateand the like.

Other flavorants and flavor intensifiers include organic acids, e.g.,acetic acid, formic acid, 2-hexenoic acid, benzoic acid, n-butyric acid,caproic acid, caprylic acid, cinnamic acid, isobutyric acid, isovalericacid, alpha-methyl-butyric acid, propionic acid, valeric acid,2-methyl-2-pentenoic acid, and 2-methyl-3-pentenoic acid; ketones andaldehydes, e.g., acetaldehyde, acetophenone, acetone, acetyl methylcarbinol, acrolein, n-butanal, crotonal, diacetyl, beta,beta-dimethyl-acrolein, n-hexanal, 2-hexenal, cis-3-hexenal, 2-heptanal,4-(p-hydroxyphenyl)-2-butanone, alpha-ionone, beta-ionone,2-methyl-3-butanone, 2-pentanone, 2-pentenal and propanal; alcohols suchas 1-butanal, benzyl alcohol, 1-borneol, trans-2-buten-1-ol, ethanol,geraniol, 1-hexanal, 2-heptanol, trans-2-hexenol-1, cis-3-hexen-1-ol,3-methyl-3-buten-1-ol, 1-pentenol, 1-penten-3-ol,p-hydroxyphenyl-2-ethanol, isoamyl alcohol, fenchyl alcohol, isofenchylalcohol, phenyl-2-ethanol, alpha-terpineol, cisterpineol hydrate;esters, such as butyl acetate, ethyl acetate, ethyl acetoacetate, ethylbenzoate, ethyl butyrate, ethyl caproate, ethyl cinnamate, ethylcrotonate, ethyl formate, ethyl isobutyrate, ethyl isovalerate, ethylalpha-methylbutyrate, ethyl propionate, ethyl salicylate,trans-2-hexenyl acetate, hexyl acetate, 2-hexenyl butyrate, hexylbutyrate, isoamyl acetate, isopropyl butyrate, methyl acetate, methylbutyrate, methyl caproate, methyl isobutyrate, alpha-methylbutyrate,propyl acetate, amyl acetate, amyl butyrate, benzyl salicylate, dimethylanthranilate, ethyl methylphenylglycidate, ethyl succinate, isobutylcinnamate and terpenyl acetate; absolutes, such as jasmine absolute,rose absolute, orris absolute, and essential oils such as orange oil,lemon oil, Bulgarian rose oil and natural vanilla; lactones; sulfides,e.g., dimethyl sulfide and other materials such as maltol, pulegonemercaptan, α-phellandrene, ethyl maltol,2,2,4,4,6,6-hexamethyl-S-trithiane, acetoin and acetals, (e.g.,1,1-diethoxyethane, 1,1-dimethoxyethane and dimethoxymethane.)

The specific flavoring adjuvant selected for use may be either solid orliquid depending upon the desired physical form of the ultimate product,i.e., foodstuff, whether simulated or natural, and should, in any event,be capable of providing an environment in which the α-oxy(oxo) sulfidesand ethers can be dispersed or admixed to provide a homogeneous medium.In addition, selection of one or more flavoring adjuvants, as well asthe quantities thereof, will depend upon the precise organolepticcharacter desired in the finished product. Thus, in the case offlavoring compositions, ingredient selection will vary in accordancewith the foodstuff to which the flavor and aroma are to be imparted. Incontradistinction, in the preparation of solid products, e.g., simulatedfoodstuffs, ingredients capable of providing normally solid compositionsshould be selected such as various cellulose derivatives.

As will be appreciated by those skilled in the art, the amount ofα-oxy(oxo) sulfide and ether employed in a particular instance can varyover a relatively wide range whereby to its desired organoleptic effectshaving reference to the nature of the product are achieved. Thus,correspondingly, greater amounts would be necessary in those instanceswherein the ultimate food composition to be flavored is relatively blandto the taste, whereas relatively minor quantities may suffice forpurposes of enhancing the composition merely deficient in natural flavoror aroma. The primary requirement is that the amount selected beeffective, i.e., sufficient to alter the organoleptic characteristics ofthe parent composition, whether foodstuff per se or flavoringcomposition.

The use of insufficient quantities of α-oxy(oxo) sulfides and etherswill, of course, substantially vitiate any possibility of obtaining thedesired results while excess quantities prove needlessly costly and inextreme cases, may disrupt the flavor-aroma balance, thus provingself-defeating. Accordingly, the terminology "effective amount" and"sufficient amount" is to be accorded a significance in the context ofthe present invention consistent with the obtention of desired flavoringeffects.

Thus, and with respect to ultimate food compositions, it is found thatquantities of α-oxy(oxo) sulfides and ethers ranging from a small buteffective amount, e.g., about 0.1 parts per million up to about 50 partsper million by weight based on total composition (more preferably fromabout 0.2 ppm up to about 10 ppm) are suitable. Concentrations in excessof the maximum quantity stated are not normally recommended, since theyfail to prove commensurate enhancement of organoleptic properties. Inthose instances, wherein the α-oxy(oxo) sulfides and ethers are added tothe foodstuff as an integral component of a flavoring composition, itis, of course, essential that the total quantity of flavoringcomposition employed be sufficient to yield an effective α-oxy(oxo)sulfide and ether concentration in the foodstuff product.

Food flavoring compositions prepared in accordance with the presentinvention preferably contain the α-oxy(oxo) sulfide and ether inconcentrations ranging from about 0.1% up to about 15% by weight basedon the total weight of said flavoring composition.

The compositions described herein can be prepared according toconventional techniques well known as typified by cake batters and fruitdrinks and can be formulated by merely admixing the involved ingredientswithin the proportions stated in a suitable blender to obtain thedesired consistency, homogeneity of dispersion, etc. Alternatively,flavoring compositions in the form of particulate solids can beconveniently prepared by mixing the α-oxy(oxo) sulfide and ether with,for example, gum arabic, gum tragacanth, carrageenan and the like, andthereafter spray-drying the resultant mixture whereby to obtain theparticulate solid product. Pre-prepared flavor mixed in powder form,e.g., a fruit-flavored powder mix are obtained by mixing the dried solidcomponents, e.g., starch, sugar and the like and α-oxy(oxo) sulfide andether in a dry blender until the requisite degree of uniformity isachieved.

It is presently preferred to combine with the α-oxy(oxo)sulfides andethers the following adjuvants:

p-Hydroxybenzyl acetone;

Geraniol;

Acetaldehyde;

Maltol;

Ethyl methyl phenyl glycidate;

Benzyl acetate;

Dimethyl sulfide;

Vanillin;

Methyl cinnamate;

Ethyl pelargonate;

Methyl anthranilate;

Isoamyl acetate;

Isobutyl acetate;

Alpha ionone;

Ethyl butyrate;

Acetic acid;

Gamma-undecalactone;

Naphthyl ethyl ether;

Diacetyl;

Ethyl acetate;

Anethole;

Isoamyl butyrate;

Cis-3-hexenol-1;

2-Methyl-2-pentenoic acid;

Elemecine (4-allyl-1,2,6-trimethoxy benzene);

Isoelemecine (4-propenyl-1,2,6-trimethoxy benzene);

2-(4-hydroxy-4-methylpentyl) norbornadiene prepared according to U.S.Application for Letters Patent 461,703 fuled on Apr. 17, 1974;

Natural blackcurrant juice;

Buchu leaf oil;

α-phellandrene;

Cis-3-hexene-1-ol;

Terpinenol-4;

Ethyl maltol;

Methyl benzoate;

Benzaldehyde;

Coriander oil;

α-ionone;

Ethyl heptanoate;

Methyl anthranilate;

Ethyl anthranilate;

Cinnamic alcohol;

Amyl valerinate;

Cinnamyl propionate;

Rhodinyl acetate;

Methyl β-hydroxy butyrate;

Ethyl β-hydroxy butyrate;

2-phenyl-3-carboethoxyfuran;

Cyclohexyl disulfide;

Grapefruit oil;

Nootkatone;

Bergamot oil;

Citral;

Amyl alcohol;

5-phenyl-4-pentenal;

5-phenyl-2-pentenal;

Allyl caproate;

2-(n-pentyl)thiazole;

2-(i-butyl) thiazole;

2-(i-propyl) thiazole;

2-(n-propyl) thiazole;

2-phenyl-4-pentenal;

2-phenyl-4-pentenaldimethylacetal;

Methional;

4-methylthiobutanal;

2-ethyl-3-acetylpyrazine;

Tetramethyl pyrazine;

2-methyl pyrazine;

trans-2-hexenal;

Hydrolyzed vegetable protein;

Monosodium glutamate;

Dimethyl disulfide;

Methyl propyl disulfide;

Methyl propenyl disulfide;

Methyl allyl disulfide;

Allyl propyl disulfide;

Propyl propenyl disulfide;

Dipropyl disulfide;

Diallyl disulfide;

Propyl propenyl trisulfide;

Thiopropanal-S-oxide;

Thiobutanal-S-oxide;

Thioethanal-S-oxide;

Thiohexanal-S-oxide; and

Propyl propene thiosulfonate.

The following examples are given to illustrate embodiments of theinvention as it is presently preferred to practice it. It will beunderstood that these examples are illustrative and that the inventionis not to be considered as restricted thereto except as indicated in theappended claims.

EXAMPLE I (A) PREPARATION OF 3-CHLORO-4-HEPTANONE ##STR34##

Into a 3000 ml, three-necked, round-bottom flask, equipped withmechanical stirrer, 500 ml addition funnel, Y-tube, pot thermometer andgas outlet tube with rubber tubing leading over a stirring solution of10% sodium hydroxide is added 1000g 4-heptanone. Addition of 434 g ofSO₂ Cl₂ drop-wise into the 4heptanone is commenced while maintaining thepot temperature in the range of 22°-34° C. and is continued over aperiod of 2 hours. A water aspirator vacuum is applied to the reactionmass in order to pull the acidic gases; sulfur dioxide and hydrogenchloride, over the sodium hydroxide solution.

The reaction mass is periodically sampled using GLC analysis until suchtime as about 25% chlorinated ketone product is found to be present.

While maintaining the reaction mass at 15° C., 1000 ml saturated sodiumchloride is added to the mixture, and the mixture is then stirred for aperiod of 10 minutes. The reaction mass is then transferred to a 5-literseparatory funnel and shaken well, whereupon the organic and aqueousphases separate. The lower aqueous phase (approximately 1000 ml) has apH of about 1. The upper organic phase is washed with 700 ml saturatedsodium bicarbonate solution to a pH of 6-7. The organic phase is thendried over 50 grams anhydrous sodium sulfate and filtered yielding ayellow oil weighing 1063 grams. The organic layer is determined tocontain 24.9% chlorinated ketone and 68.1% original ketone startingmaterial. This material is then vacuum distilled by first adding it to a2000 ml, three-necked, round-bottom flask equipped with a 2.5 × 60 cmvacuum jacketed column packed with 6 mm Raschig Rings, and equipped withan automatic reflux head, a pot thermometer, a heating mantle, a vacuumpump and a dry-ice trap. Fractionation data is as follows:

    ______________________________________                                        Vacuum Pot     Vapor   Weight of                                              (mmHg) Temp.   Temp.   Fraction                                                                              Cut. No.                                                                             Reflux Ratio                            ______________________________________                                        62     80      71      51.0 g  1      60:40                                   62     81.5    71      149.0 g 2      40:60                                   58     82.5    70      157.5 g 3      30:70                                   59     89.5    70      175.0 g 4      30:70                                   59     96      75      110 g   5      30:70                                   59     100     80      24.5 g  6      50:50                                   58     101     90      16.0 g  7      50:50                                   58     102     94      37.5 g  8      30:70                                   55     103     94      144.5 g 9      30:70                                   54     110     95      85.0 g  10     30:70                                   54     119      102    28.0 g  11     30:70                                   15     140     80      45.0 g  12     30:70                                   ______________________________________                                    

GLC analysis on each of cuts 5-12 (conditions 8' × 1/4" SE-30 column)yields the following information:

    __________________________________________________________________________          Percent                                                                            Percent                                                                             Percent                                                            low  4-    3-Cl   Percent High                                                                         Percent High                                                                         Percent High                                                                         Percent High                     Cut No.                                                                             Boilers                                                                            Heptanone                                                                           4-Heptanone                                                                          Boiler (A)                                                                           Boiler (B)                                                                           Boiler (C)                                                                           Boiler(D)                        __________________________________________________________________________    5     0.09 96.15 2.97   --     --     --     --                               7          50%   50%                                                          8     --   9.28  87.09  2.43   0.57   --     --                               9     --   trace 95.78  3.22   1.00   --     --                               10    --   --    91.38  4.89   3.34   0.21   --                               11    --   --    69.14  7.27   19.88  3.71   --                               12    --   --    8.32   2.07   49.28  39.69  0.47                             __________________________________________________________________________

Cuts 8, 9 and 10 are blended (weight 266.5 gms) and are analyzed asfollows:

    ______________________________________                                        0.95%         4-heptanone                                                     93.89%        3-chloro-4-heptanone                                            3.60%         high boiler A                                                   1.57          high boiler B                                                   ______________________________________                                    

EXAMPLE I(B) PREPARATION OF 3-THIOACETYL-4-HEPTANONE ##STR35##

Into a 25 ml, three-necked, round-bottom flask equipped with magneticstirrer, nitrogen inlet tube, 6 inches Vigreux column with cotton plugand pot thermometer is added a solution of 0.27 grams sodium methoxidein 3 ml anhydrous methanol (0.005 moles sodium methoxide). Under drynitrogen, 0.38 grams of thioacetic acid dissolved in 3 ml anhydrousmethanol (0.005 moles thioacetic acid) is then added to the sodiummethoxide solution over a 2-minute period. A solution of3-chloro-4-heptanone in methanol (0.75 grams 3-chloro-4-heptanonedissolved in one ml anhydrous methanol) prepared according to Part A,supra, (cuts 8, 9 and 10 blended) is then added to the reaction masswhich becomes turbid. Stirring is continued for a period of one hour,whereupon GLC analysis (conditions: 8 feet × 1/4 inch SE-30 column)yields the following data:

    ______________________________________                                        15.6%          3-chloro-4-heptanone                                           3.0%           chloro heptanone high boiler                                   77.67%         major peak                                                     2.37%          late peak                                                      ______________________________________                                    

With stirring, 15 ml water is added to the reaction mass which thensplits up into two phases, an aqueous phase and an organic phase. The pHof the aqueous phase is 5-6. The organic phase is extracted with two10-ml portions of methylene chloride. The methylene chloride extractsare combined and washed with 5 ml saturated chloride solution. Theorganic phase is then dried over anhydrous sodium sulfate andconcentrated in a rotary evaporator using water aspirator vacuumyielding 0.65 grams of a dark amber oil. GLC trapping of the major peak(Conditions: 8 feet × 1/4 SE-30 column operated at 120° C., programmedat 5° C./minute yields a compound having a molecular weight of 188 andhaving a mass spectral analysis, NMR analysis and IR analysis whichcause confirmation of the structure: ##STR36##

The NMR spectrum is set forth in FIG. 1. The IR spectrum is set forth inFIG. 2.

The NMR analysis is as follows:

    ______________________________________                                        3-thioacetyl-4-hepanone                                                                        ##STR37##                                                    0.92 ppm  (t)    C --H.sub.3CH.sub.2                                                                                  6H                                    0.96      (t)    CH.sub.3CCS                                                  2.01-1.44 (m)    CH.sub.2               4H                                    2.39      (s)                                                                                   ##STR38##                                                                                           5H                                    2.53      (m)                                                                                   ##STR39##                                                   4.20      (t)    OCHCSCO                IH                                    ______________________________________                                    

the IR analysis is as follows:

620 cm⁻¹, 950, 1125, 1350, 1450, 1690, 2320, 2870, 2930, 2960.

Material prepared similarly to above example was vacuum distilledyielding 99.3% pure product (boiling point 93.5°-94.5° C. at 2.8 mm Hg).The thus-distilled material has the same physical properties as setforth above for 3-thioacetyl-4-heptanone.

PREPARATION OF 3-THIOMETHYL-4-HEPTANONE ##STR40##

Into a 50-ml, three-necked, round-bottom flask equipped with magneticstirrer, dry ice condenser, pot thermometer, cold water bath, refluxcondenser with nitrogen inlet tube and nitrogen bubbler, is placed asolution of 0.54 grams of sodium methoxide in 6 ml anhydrous methanol(0.01 moles sodium methoxide). The sodium methoxide solution is thencooled using the cold-water bath to a temperature of 25° C. The nitrogenflow is ceased and methyl mercaptan in methanol (0.48 grams methylmercaptan in 6 ml anhydrous methanol, 0.01 moles methyl mercaptan) isadded to the reaction mass while maintaining same at 24° C. At 24° C. asolution of 1.49 grams of 3-chloro-4-heptanone in 2 ml anhydrousmethanol (0.01 moles 3-chloro-4-heptanone) is added to the reactionmass. The 3-chloro-4-heptanone is produced according to the process setforth in part (A), supra. The reaction mass is maintained, withstirring, at 25° C. for a period of 1 hour and 15 minutes. At the end ofthis period, the reaction mass is flushed with nitrogen. The reactionmass is then concentrated on a rotary evaporator using a water aspiratorvacuum to approximately 5 ml.

Distilled water (15 ml) is then added to the concentrated reactionmixture whereupon the reaction mixture forms into two phases; an oilphase and an aqueous phase. The pH of the aqueous phase is in the rangeof 5-6. The oil phase is then extracted with two 12-ml portions ofn-hexane and the phases are separated. The hexane extracts are combined,washed with water (5 ml), dried over anhydrous sodium sulfate, gravityfiltered and concentrated on a rotary evaporator to a weight of 1.29grams. The resulting product contains 90.1% 3-thiomethyl-4-heptanone byGLC analysis having the structure: ##STR41## as confirmed by NMR, IR andmass spectral analyses of trapped compound.

The NMR spectrum is set forth in FIG. 3. The IR spectrum is set forth inFIG. 4.

The NMR analysis is as follows:

    ______________________________________                                        3-thiomethyl-4-heptanone                                                                       ##STR42##                                                    0.94 ppm  (t)    C --H.sub.3CH.sub.2                                                                                6H                                      0.97      (t)    CH.sub.3CCS                                                  1.68      (m)    CH.sub.2             4H                                      1.92      (s)    CH.sub.3S            3H                                      2.60      (m)                                                                                   ##STR43##           2H                                      3.08      (t)                                                                                   ##STR44##           1H                                      ______________________________________                                    

the IR analysis is as follows:

1360 cm⁻¹, 1375, 1455, 1690, 2330, 2880, 2930, 2960.

Material prepared similarly to above example was vacuum distilledyielding 99.2% pure product (boiling point 78°-78.5° C. at 8.5 mm Hg).The thus-distilled material has the same physical properties as setforth above for 3-thiomethyl-4-heptanone.

(D) PREPARATION OF 3-THIOMETHYL-4-HEPTANOL ##STR45##

Into a 25 ml, three-necked, round-bottom flask equipped with magneticstirrer, nitrogen inlet tube, reflux condenser, pot thermometer, andcold water bath, is added a solution of 0.10 grams sodium borohydride(NaBH₄) dissolved in 4 ml anhydrous ethyl alcohol (0.00265 moles sodiumborohydride). While maintaining the pot temperature at 25° C., asolution of 0.8 grams of 3-thiomethyl-4-heptanone in 3.5 ml anhydrousethyl alcohol is added to the sodium borohydride-ethanol solution over aone-minute period. The reaction mass then warms up to about 30° C. andis maintained at a temperature of between 25° and 30° C. for a period ofabout 1.5 hours. At the end of this period another 0.05 grams (0.00133moles) of sodium borohydride and 2 ml ethanol is added.

After 10 minutes of stirring while maintaining the reaction mass at 25°C., the reaction mass is then worked up as follows. The reaction mixtureis concentrated to about 4 ml of a thick slurry using water aspiratorvacuum. The resulting thick slurry is then combined with 12 ml waterthereby causing the solid to dissolve, and the reaction mass to exist intwo phases; an aqueous phase and an organic phase. The aqueous phase isacidified to a pH of 2-3 using 10% HCl solution. The organic phase isextracted with two 12-ml portions of methylene chloride. The extractsare then combined, washed with 8 ml water, dried over anhydrous sodiumsulfate, gravity filtered, and then concentrated on a rotary evaporator(using water aspirator vacuum) to a weight of 0.58 grams. The desiredproduct is trapped out on a 8 feet × 1/4 inch SE-30 GLC column, and MS,NMR and IR analyses confirm that the resulting compound has thestructure: ##STR46##

The NMR spectrum is set forth in FIG. 5. The infrared spectrum is setforth in FIG. 6.

The NMR analysis is as follows:

    ______________________________________                                        0.94 ppm (t)       C --H.sub.3CH.sub.2                                                                          6H                                          1.06     (t)       CH.sub.3CCS                                                1.51     (m)       CH.sub.2       6H                                          2.06     (s)       CH.sub.3S      3H                                          2.36     (m)       HCS                                                                                          2H                                          2.62     (broad)   OH                                                         3.52     (m)       HCO            1H                                          ______________________________________                                    

The IR analysis is as follows:

980 cm⁻¹, 1010, 1065, 1370, 1430, 1450, 2320, 2860, 2920, 3440.

Material prepared similarly to above example was vacuum distilledyielding 99.5% pure product (boiling point 64°-64.5° C. at 1.5 mm Hg).The thus-distilled material has the physical properties as set forthabove for 3-thiomethyl-4-heptanol.

EXAMPLE II PREPARATION OF 3-METHALLYLTHIO-2,6-DIMETHYL-4-HEPTANONE (A)Preparation of 3-chloro-2,6-dimethyl-4-heptanone Reaction: ##STR47##

Into a one-liter, three-necked, round bottom flask equipped with "Y"tube, pot thermometer, mechanical stirrer, 125 ml addition funnel, gasoutlet tube, cold water bath and water aspirator vacuum is added 356grams of 2,6-dimethyl-4-heptanone (2.4 moles). Over a period of onehour, 67.5 grams (40 ml; 0.5 moles) of SO₂ Cl₂ is slowly added to theketone with stirring while maintaining the reaction mass temperature inthe range of 23°-35° C.

The reaction mass is then evacuated slowly using water aspirator vacuumthereby removing most of the acidic gases resulting from the foregoingreaction.

The reaction mass is then transferred to a one-necked, one-liter,round-bottom flask and the last traces of acidic gases are removed thusyielding 371 grams of product. The reaction mass is then transferred toa 500 ml, three-necked, round-bottom flask equipped with a 2.0 × 30 cmcolumn packed with 1/8 inch helices, reflux head, magnetic stirrer,heating mantle and vacuum pump, and the resulting3-chloro-2,6-dimethyl-4-heptanone is fractionally distilled at a vaportemperature of 106°-107° C. and a pressure of 45-46 mm Hg yielding aproduct of 97% purity as confirmed by GLC, mass spectral, NMR and IRanalyses.

B. Preparation of 3-mercapto-2,6-dimethyl-4-heptanone ##STR48##

Into a 250 ml, round bottom, three-necked flask equipped with magneticstirrer, pot thermometer, 6 inch Vigreux distillation column with gasoutlet at top leading over 200 ml 10% sodium hydroxide solution, H₂ Sgas inlet tube (sub-surface), "Y" tube, 50 ml addition funnel, gasbubbler, and dry ice-isopropyl alcohol bath, and cold water bath isadded a solution of 11.6 grams of sodium methoxide dissolved in 90 mlanhydrous methanol. The sodium methoxide solution is cooled to atemperature of -15° C. using the dry ice-isopropanol bath. Whilemaintaining the temperature of the sodium methoxide solution at -10° to-5° C., hydrogen sulfide is bubbled into the reaction mass over a periodof 2 hours. While continuing to bubble in hydrogen sulfide andmaintaining the reaction mass at a temperature in the range of -5° to-9° C., the 3-chloro-2,6-dimethyl-4-heptanone prepared in Part A of thisexample (18.2 grams; 0.100 moles) is added slowly to the reaction massfrom the addition funnel over a period of 13 minutes. The reaction massis then maintained at a temperature of 0°-26° C. for a period of 4 hours(25° C.-26° C. for the last 1.5 hours).

The reaction mass is then concentrated to approximately 25 ml (thickslurry) using a rotary evaporator and water aspirator vacuum. 85 mldistilled water is then added to the reaction mass, with stirring, whilemaintaining the temperature at 25° C., thereby yielding a turbid yellowsolution. 85 grams of 10% aqueous sodium hydroxide is then added to theresulting mixture whereupon the temperature rises from 25° C. to 28° C.(pH = 10-11). The basic aqueous solution is then extracted with two 70ml portions of methylene chloride and the extracts are combined, driedand concentrated yielding 1.7 grams of an oil. The basic aqueoussolution is then acidified with 115 ml 10% hydrochloride acid to a pH of1-2. This is then extracted with four 50 ml portions of methylenechloride. The methylene chloride extracts are combined and washed withtwo 35 ml portions of saturated sodium chloride (to a pH of 5) and driedover anhydrous sodium sulfate. The resulting mixture is gravity filteredand concentrated on a rotary evaporator to yield 15.5 grams of productcontaining 96.1% 3-mercapto-2,6-dimethyl-4-heptanone as confirmed bymass spectral, NMR and IR analyses. This material is vacuum distilled ata vapor temperature of 77.5°-78° C. and a pressure of 6 mm Hg.

C. Preparation of 3-methyallylthio-2,6-dimethyl-4-heptanone ##STR49##

Into a 25 ml, three-necked, round-bottom flask equipped with magneticstirrer, "Y" tube, nitrogen inlet, reflux condenser with cotton plug,cold water bath and warm water bath is added a solution of 0.162 gramsof sodium methoxide dissolved in 2 ml anhydrous methanol. Over a periodof 1 minute is added a solution of 0.522 grams of3-mercapto-2,6-dimethyl-4-heptanone dissolved in 3 ml anhydrousmethanol, with stirring. After stirring for 12 minutes at 24°-25° C., asolution of 0.3 grams of 3-chloro-2-methylpropene in 1 ml anhydrousmethanol is added. With a water bath the resulting reaction mass iswarmed to 31° C. and the reaction mass is then stirred while maintainingthe temperature in the range of 23°-30° C. for a period of 2 hours.

The reaction mass is then concentrated on a rotary evaporator usingwater aspirator vacuum to approximately 4 ml yielding a slurry. To theslurry is added 8 ml water and the solid dissolves. The reaction mass isthen acidified to a pH of 1-2 with 3 drops of 10% hydrochloric acid. Thereaction mass is then extracted with three 8 ml portions of methylenechloride and the extracts are combined and washed with 10 ml water,dried over anhydrous sodium sulfate and gravity filtered. The extractsare concentrated on a rotary evaporator to yield 0.54 grams of a whiteoil containing 93.6% by GLC of 3-methallylthio-2,6-dimethyl-4-heptanoneas confirmed using MS, IR and NMR analyses of trapped product.

The NMR spectrum is set forth in FIG. 7. The infrared spectrum is setforth in FIG. 8.

The mass spectral analysis is as follows:

    ______________________________________                                        m/e             Relative Intensity                                            ______________________________________                                        41              29                                                            55              44.sup.3                                                      57              37.sup.6                                                      69              10                                                            85              43.sup.5                                                      87              93.sup.2                                                      109             33                                                            142             44.sup.4                                                      143             100.sup.1                                                     M 288           28                                                            ______________________________________                                    

The NMR analysis is as follows:

    ______________________________________                                        1.92 ppm, 2.06                                                                           (2 doublets)                                                                               ##STR50##   12H                                       1.78       (s)         CCH.sub.3    3H                                        2.12       (m)         methine protons                                                                            2H                                        2.47       (t)         CH.sub.2     2H                                        2.82       (d)                                                                                        ##STR51##   1H                                        3.01       (s)         CCH.sub.2S   2H                                        4.86       (s)                                                                                        ##STR52##   2H                                        ______________________________________                                    

the IR analysis is as follows:

890 cm⁻¹, 1035, 1160, 1200, 1225, 1285, 1360, 1380, 1400, 1460, 1640,1695, 2870, 2960, 3080.

Material prepared similarly to above example was vacuum distilledyielding 99.8% pure product (boiling point 100°-100.5° C. at 1.3 mm Hg).The thus-distilled material has the same physical properties as setforth above for 3-methallylthio-2,6-dimethyl-4-heptanone.

D. PREPARATION OF 3-CROTYLTHIO-2,6-DIMETHYL-4-HEPTANONE ##STR53##

Into a 25 ml, three-necked, round bottom flask equipped with magneticstirrer, reflux condenser, nitrogen inlet tube and cold water bath isplaced a solution of 0.162 grams (0.003 moles) of sodium methoxidedissolved in 2 ml anhydrous methanol. Using the cooling bath thetemperature of the sodium methoxide solution is cooled to 23° C. atwhich point a solution of 0.52 grams (0.003 moles) of3-mercapto-2,6-dimethyl-4-heptanone in 2 ml anhydrous methanol is addedto the sodium methoxide solution. While maintaining the temperature ofthe reaction mass at 24°-29° C. and over a period of 2 minutes, asolution of 0.300 grams of 80% crotyl chloride dissolved in 2 mlanhydrous methanol (0.0026 moles crotyl chloride) is added to thereaction mass with stirring. The reaction mass is continued to bestirred for a period of 2.5 hours and is then concentrated on a rotaryevaporator using water aspirator vacuum to 2 ml product (solid/ oilslurry). Nine ml water is added to the reaction mass thereby dissolvingthe solid. The oil is extracted with three 8 ml portions of methylenechloride and the extracts are combined and washed with 6 ml water. Themethylene chloride extracts are then dried over anhydrous sodiumsulfate, gravity filtered and concentrated on a rotary evaporator to0.59 grams pale-yellow oil. The major product is isolated using GLCapparatus (8 foot × 1/4 inch Carbowax column). NMR, mass spectral and IRanalyses yield the information that the resulting material is3-crotylthio-2,6-dimethyl-4-heptanone having the structure: ##STR54##

The NMR spectrum is set forth in FIG. 9. The infrared spectrum is setforth in FIG. 10.

The mass spectral analysis is as follows:

    ______________________________________                                        m/e             Relative Intensity                                            ______________________________________                                        41              20                                                            55              90.sup.2                                                      57              37.sup.5                                                      85              36.sup.6                                                      87              100.sup.1                                                     89              33                                                            141             22                                                            142             45.sup.4                                                      143             63.sup.3                                                      M 228           13                                                            ______________________________________                                    

The NMR analysis is as follows:

    ______________________________________                                        0.84 ppm, 1.08                                                                            (doublets) CH.sub.3--     12H                                     1.70        (d)        =C--CH.sub.3   3H                                      2.14        (m)        methine protons                                                                              2H                                      2.48        (m)        --CH.sub.2 --C=O                                                                             2H                                      2.82        (d)        O=C--HC--S--   1H                                      2.99        (m)        =C--CH.sub.2 --S--                                                                           2H                                      5.50        (m)        olefinic protons                                                                             2H                                      ______________________________________                                    

The infrared analysis is as follows:

960 cm⁻¹, 1035, 1135, 1160, 1285, 1360, 1380, 1400, 1465, 1695, 2870,2930, 2960, 3020.

E. PREPARATION OF 3-ALLYLTHIO-2,6-DIMETHYL-4-HEPTANONE ##STR55##

Into a 25 ml, round bottom, three-necked flask equipped with magneticstirrer, reflux condenser, nitrogen inlet tube and cold water bath isplaced a solution of 0.162 grams (0.003 moles) of sodium methoxidedissolved in 2 ml anhydrous methanol. Using the water bath thetemperature of the sodium methoxide solution is reduced to 23° C. At 23°C., a solution of 0.522 grams (0.003 moles) of3-mercapto-2,6-dimethyl-4-heptanone dissolved in 3 ml anhydrous methanolis added to the sodium methoxide solution. Subsequent to the addition ofthe mercapto ketone, after stirring for 15 minutes at 23° C., a solutionof 0.40 grams (0.0033 moles) of allyl bromide dissolved in 2 mlanhydrous methanol is added to the reaction mass with stirring. Thereaction mass warms to 33° C. and is continued to be stirred at 25°-33°C. for a period of 2 hours. It is concentrated on a rotary evaporatorusing water aspirator vacuum to a volume of 3 ml, thus yielding a whiteslurry. Eight ml water is then added to the slurry thereby dissolvingthe solid therein. One drop of 10% HCl is added to the resultingmaterial thereby reducing the pH from about 9 to about 5. The reactionmass now existing in two phases is extracted with three 8 ml volumes ofmethylene chloride. The extracts are combined and washed with 6 ml waterand then dried over anhydrous sodium sulfate, gravity filtered andconcentrated on a rotary evaporator to a weight of 0.55 grams (paleyellow oil). GLC analysis (8 feet × 1/4 inch SE-30 column), NMR, IR andmass spectral analyses of GLC isolated material confirm that theresulting product is 97% product, 3-allylthio-2,6-dimethyl-4-heptanone,having the structure: ##STR56##

The NMR spectrum is illustrated in FIG. 11. The infrared spectrum isillustrated in FIG. 12.

The mass spectral analysis is as follows:

    ______________________________________                                        m/e             Relative Intensity                                            ______________________________________                                        41               33.sup.5                                                     55              24                                                            57               32.sup.6                                                     69              18                                                            73               40.sup.3                                                     85              30                                                            87               43.sup.2                                                     95              30                                                            129             100.sup.1                                                     142              38.sup.4                                                     M 214           17                                                            ______________________________________                                    

The NMR analysis is as follows:

    ______________________________________                                        0.84 ppm, 1.08                                                                           (doublets)  CH.sub.3       12H                                     2.14       (m)         methine protons                                                                              2H                                      2.48       (m)         CH.sub.2CO     2H                                      2.84       (d)         CHCS           1H                                      3.04       (m)         CCH.sub.2S     2H                                      5.22-5.04  (m)                                                                                        ##STR57##     2H                                      5.96-5.56  (m)                                                                                        ##STR58##     1H                                      ______________________________________                                    

the IR analysis is as follows:

914 cm⁻¹, 980, 1035, 1160, 1360, 1380, 1465, 1695, 2870, 2930, 2960.

F. PREPARATION OF (1,3-DIETHYL ACETONYL) (1,3-DIISOPROPYLACETONYL)SULFIDE ##STR59##

Into a 50 ml, round bottom, three-necked flask equipped with magneticstirrer, pot thermometer, "Y" tube, nitrogen inlet tube, refluxcondenser with cotton plug, and water bath is placed a solution of 0.65grams (0.012 moles) of sodium methoxide dissolved in 10 ml anhydrousmethanol. While maintaining the temperature of the reaction mass at24°-27° C., a solution of 2.1 grams of3-mercapto-2,6-dimethyl-4-heptanone dissolved in 12 ml anhydrousmethanol is added to the sodium methoxide solution. 1.78 grams of3-chloro-4-heptanone is then added to the reaction mass with stirringover a period of 2 minutes, the reaction mass temperature rising to 38°C. Two ml anhydrous methanol used as rinse is then added to the reactionmass, and with stirring the reaction mass temperature cools to 25° C.The reaction mass is continued to be stirred at 25° C. for a period of 5hours. At this point 25 ml distilled water is added, and the resultingsolid dissolves. The oil phase is extracted with three 15 ml portions ofmethylene chloride, and the extracts are combined and washed with one 10ml portion of water. The extracts are then dried over anhydrous sodiumsulfate and gravity filtered and concentrated on a rotary evaporatorusing water aspirator vacuum to a weight of 3.20 grams (yellow oil). GLCanalysis (8 feet × 1/4 inches SE-30 column), NMR, IR and mass spectralanalyses of GLC isolated material yield the information that theresulting product is 85% pure and has the structure: ##STR60##

The NMR spectrum is set forth in FIG. 13. The IR spectrum is set forthin FIG. 14.

The mass spectral analysis is as follows:

    ______________________________________                                        m/e             Relative Intensity                                            ______________________________________                                        41              50.sup.6                                                      43              82.sup.3                                                      55              33                                                            57              89.sup.2                                                      71              56.sup.5                                                      85              100.sup.1                                                     114             67.sup.4                                                      145             39                                                            201             36                                                            M 286           29                                                            ______________________________________                                    

The NMR analysis is as follows:

    ______________________________________                                        1.07 ppm, 0.86                                                                           CH.sub.3            18H                                            1.62       CH.sub.2 + methine protons                                                                        6H                                             2.46       CH.sub.2CO          4H                                             3.15 and 2.96                                                                             ##STR61##          2H                                             ______________________________________                                    

the IR analysis is as follows:

1155 cm⁻¹, 1360, 1380, 1460, 1700, 2870, 2930, 2960.

G. PREPARATION OF3-[(METHOXYCARBONYL)METHYLTHIO]-2,6-DIMETHYL-4-HEPTANONE ##STR62##

Into a 50 ml, round-bottom, three-necked flask equipped with magneticstirrer, pot thermometer, "Y" tube, nitrogen inlet tube, refluxcondenser with cotton plug, H₂ SO₄ bubbler for nitrogen, and cold waterbath is added a solution of 0.65 grams of sodium methoxide dissolved in10 ml anhydrous methanol. At a reaction mass temperature of 25°-28° C.and over a period of 1 minute, with stirring, is added a solution of 2.1grams of 3-mercapto-2,6-dimethyl-4-heptanone dissolved in 2 ml anhydrousmethanol. After stirring 8 minutes, 1.30 grams of methylchloroacetate(0.012 moles) is added over a period of 2 minutes, to the reaction mass;the temperature of the reaction mass rising to 38° C. The reaction massis allowed to cool to 24° C. and is stirred for a period of 2 hours.

Distilled water (25 ml) is then added to the reaction mass whereupon thesolid present dissolves. The organic phase is then extracted with three15 ml methylene chloride portions. The combined extracts are washed withone 10 ml portion of water and dried over anhydrous sodium sulfate andgravity filtered. The filtered extracts are then concentrated on arotary evaporator using water aspirator vacuum to a weight of 2.67 grams(pale yellow oil). GLC trapping of the major component (conditions: 8feet × 1/4 inches SE-30 column), with mass spectral, IR and NMR analysesconfirm that the resulting product has the structure: ##STR63##

The NMR analysis is as follows:

    ______________________________________                                        0.94, 1.10 ppm                                                                            ##STR64##      12H                                                2.12                                                                                      ##STR65##      2H                                                 2.50                                                                                      ##STR66##      2H                                                 3.03                                                                                      ##STR67##      1H                                                 3.19                                                                                      ##STR68##      2H                                                 3.70                                                                                      ##STR69##      3H                                                 ______________________________________                                    

the IR analysis is as follows:

1145 cm⁻¹, 1185, 1285, 1360, 1375, 1430, 1460, 1695, 1735, 2860, 2920,2960.

The mass spectral analysis is as follows:

    ______________________________________                                        m/e             Relative Intensity                                            ______________________________________                                        29              11                                                            41               24.sup.6                                                     43              12                                                            55              24                                                            57               53.sup.3                                                     85               46.sup.4                                                     101             100.sup.1                                                     129              32.sup.5                                                     161              75.sup.2                                                     M 246           21                                                            ______________________________________                                    

The NMR spectrum is set forth in FIG. 14(A). The infrared spectrum isset forth in FIG. 14(B).

(H) PREPARATION OF 3-[(METHOXYCARBONYL)METHYLTHIO]-4-HEPTANONE

Reaction: ##STR70##

Into a 50 ml, three-necked, round bottom flask equipped with magneticstirrer, pot thermometer, "Y" tube, nitrogen inlet tube, refluxcondenser with cotton plug and cold water bath is placed a solution of1.08 grams of sodium methoxide dissolved in 11 ml anhydrous methanol(0.02 moles sodium methoxide). Over a period of 2 minutes and at atemperature of 25°-30° C., 2.12 grams (0.02 moles) of methylthioglycolate dissolved in 2 ml anhydrous methanol is added to thereaction mass with stirring. After 5 minutes, 2.97 grams of3-chloro-4-heptanone is then added to the reaction mass with stirringwhile the temperature of the reaction mass warms to 40° C. The reactionmass then cools to 35° C. and is stirred in the temperature range of25°-35° C. for a period of 2 1/2 hours.

25 ml water is then added to the reaction mass with stirring, and thesolid present therein dissolves (pH = 6-7). The reaction mass isextracted with three 20 ml volumes of methylene chloride, and themethylene chloride extracts are combined and washed with one 10 mlportion of water. The methylene chloride extracts are then dried overanhydrous sodium sulfate, gravity filtered and concentrated on a rotaryevaporator using water aspirator vacuum to a weight of 3.77 grams (lightyellow oil). GLC analysis (conditions: 8 feet × 1/4 inches SE-30 column)indicates 92.0% product. NMR, mass spectral and IR analyses of GLCisolated material confirm that the resulting product is: ##STR71##

The mass spectral analysis is as follows:

    ______________________________________                                        m/e             Relative Intensity                                            ______________________________________                                        27              11                                                            41              21                                                            43              54.sup.4                                                      45              12                                                            55              11                                                            71              59.sup.3                                                      87              100.sup.1                                                     115             41.sup.5                                                      147             90.sup.2                                                      M 218           35.sup.6                                                      ______________________________________                                    

The NMR analysis is as follows:

    ______________________________________                                        0.98 ppm   methyl protons  6H                                                 2.06-1.46  CH.sub.2        4H                                                 2.60       CH.sub.2CO      2H                                                 3.22       SCH.sub.2CO                                                                                   3H                                                 3.30       OCHCS                                                              3.72                                                                                      ##STR72##      3H                                                 ______________________________________                                    

the IR analysis is as follows:

1000 cm⁻¹, 1150, 1185, 1275, 1430, 1450, 1695, 1730, 2860, 2920, 2960.

The NMR spectrum is set forth in FIG. 15. The infrared spectrum is setforth in FIG. 16.

EXAMPLE III A. Preparation of 3-propylthio-4-heptanone ##STR73##

Into a 50 ml, three-necked, round bottom flask equipped with magneticstirrer, reflux condenser, nitrogen inlet tube pot thermometer and coldwater bath, is placed a solution of 0.54 grams of sodium methoxidedissolved in 6 ml anhydrous methanol (0.01 moles of sodium methoxide).The sodium methoxide solution is cooled using the water bath to 25° C. Asolution of 0.76 grams of n-propyl mercaptan dissolved in 6 ml anhydrousmethanol (0.01 moles of n-propyl mercaptan) is then added to the sodiummethoxide/methanol solution, and the temperature rises to 28° C. 1.5 g(0.01 moles) 3-chloro-4-heptanone dissolved in 2 ml anhydrous methanolis then added, and the temperature of the reaction mass rises to 38° C.,whereupon it is cooled using the water bath to a temperature in therange of 25°-30° C. The reaction mass is then stirred under nitrogen fora period of 6 hours.

The reaction mass is then concentrated to a volume of 4 ml using arotary evaporator to which water aspirator vacuum is applied. 9 mldistilled water is then added to the reaction mass concentrate whereuponthe solid dissolves. The oil phase is extracted with three 8 ml portionsof methylene chloride, and the extracts are combined and washed with 8ml of water and dried over anhydrous sodium sulfate and filtered andthen concentrated. GLC, MS, NMR and IR analyses yield the informationthat the subject material is 3-propylthio-4-heptanone.

The NMR spectrum is set forth in FIG. 17. The IR spectrum is set forthin FIG. 18.

The NMR analysis is as follows:

    ______________________________________                                        0.87-1.04 ppm                                                                             superimposed                                                                             CH.sub.3 --   9H                                                   signals                                                           1.63        (m)        CH.sub.2      6H                                       2.38        (t)        CH.sub.2S     2H                                       2.60        (t)                                                                                       ##STR74##    2H                                       3.11        (t)        OCHCS         1H                                       ______________________________________                                    

the IR analysis is as follows:

1130 cm⁻¹, 1165, 1290, 1360, 1380, 1405, 1460, 1700, 2880, 2940, 2960

The mass spectral analyses is as follows:

    ______________________________________                                        m/e      Relative Intensity                                                   ______________________________________                                        41       20.sup.4                                                             43       26.sup.3                                                             55       5                                                                    71       10                                                                   75       35.sup.2                                                             114      10                                                                   117      100.sup.1                                                            118      10.sup.6                                                             119      9                                                                    M 188    16.sup.5                                                             ______________________________________                                    

Material prepared similarly to above example was vacuum distilledyielding 98.4% pure product (boiling point 72°-73° C. at 1.5 mm Hg). Thethus-distilled material has the same physical properties as set forthabove for 3-propylthio-4-heptanone.

B. Preparation of 3-propylthio-4-heptanol ##STR75##

Into a 25 ml, three-necked, round bottom flask equipped with magneticstirrer, reflux condenser, pot thermometer, and nitrogen inlet (forflushing with dry nitrogen) is added a solution of 0.15 grams of sodiumborohydride dissolved in 6 ml anhydrous methanol (0.004 moles sodiumborohydride). With stirring, a solution of 1.0 grams of3-propylthio-4-heptanone dissolved in 4 ml anhydrous ethyl alcohol isadded to the sodium borohydride solution which then warms to 28° C. Thereaction mass is stirred for a period of 2 hours at 25° C. and thenconcentrated on a rotary evaporator (using water aspirator vacuum) to avolume of 4 ml yielding an oily solid. 8 ml water is then added to thesolid, with stirring, and the solid dissolves yielding two phases: anoil phase and a water phase. The resulting reaction mass is acidifiedwith 10% hydrochloric acid to a pH of between 2 and 3. The oil phase isextracted with three 8 ml volumes of methylene chloride, and theextracts are combined and washed with 8 ml water. The extracts are thendried over anhydrous sodium sulfate, filtered and concentrated to aweight of 0.79 grams (water-white oil). GLC, IR, mass spectral and NMRanalyses after GLC trapping (conditions: 8 feet × 1/4 inches SE-30column) yield the information that the crude is 96% product having thestructure 3-propylthio-4-heptanol.

The NMR spectrum is set forth in FIG. 19. The IR spectrum is set forthin FIG. 20.

The NMR analysis is as follows:

    ______________________________________                                        1.13-0.96 ppm                                                                            superimposed                                                                              methyl protons                                                                             9H                                                   signals                                                            1.44       (m)         --CH.sub.2 --                                                                              8H                                        2.47       (s)         --OH                                                                                       4H                                        2.49       (m)         HC--S--CH.sub.2 --                                     3.50       (m)         HC--O--      1H                                        ______________________________________                                    

The IR analysis is as follows:

1290 cm⁻¹, 1380, 1460, 2880, 2940, 2970, 3460.

Material prepared similarly to above example was vacuum distilledyielding 99.8% pure product (boiling point 65° C. at 0.4 mm Hg). Thethus-distilled material has the same physical properties as set forthabove for 3-propylthio-4-heptanol.

EXAMPLE IV PREPARATION OF 3-ISOBUTYLTHIO-4-HEPTANONE ##STR76##

Into a 50 ml, three-necked, round bottom flask equipped with magneticstirrer, reflux condenser, pot thermometer, water bath, 15 cm Vigreuxcolumn with nitrogen inlet at top is added a solution of 0.54 grams ofsodium methoxide (0.01 moles) in 6 ml anhydrous methanol. The reactionmass is cooled to 25° C. and a solution of 0.90 grams of isobutylmercaptan (2-methyl-1- propanethiol) dissolved in 6 ml anhydrousmethanol is added over a period of 1 minute. After keeping the reactionmass at 24° C. with stirring for a period of 10 minutes, 1.50 grams of3-chloro-4-heptanone dissolved in 2 ml anhydrous methyl alcohol (0.01moles of 3-chloro-4-heptanone) is added to the reaction mass which thenwarms to 37° C. The reaction mass is allowed to cool to a temperature of24° C. and stirred at that temperature for a period of 6 hours.

The reaction mass is then concentrated on a rotary evaporator usingwater aspirator vacuum to a volume of 4 ml yielding an oily solid. Tenml water is then added, and the solid dissolves yielding two phases: anoil phase and an aqueous phase. The oil phase is extracted with three 9ml portions of methylene chloride, and the extracts are combined andwashed with 9 ml water. The extracts are then dried over anhydroussodium sulfate, filtered and concentrated to a weight of 1.78 grams.

Mass spectral, infrared, NMR and IR analyses yield the information thatthe reaction mass contains 90.9% product which is3-isobutylthio-4-heptanone.

The NMR spectrum is set forth in FIG. 21. The IR spectrum is set forthin FIG. 22.

The NMR analysis is as follows:

    ______________________________________                                        0.96 ppm (d)                                                                                    ##STR77##                                                   0.98     (t)     CH.sub.3CH.sub.2     12H                                     0.91     (t)                                                                                    ##STR78##                                                   1.70     (m)                                                                                    ##STR79##           5H                                      2.26     (d)     SCH.sub.2            2H                                      2.60     (t)                                                                                    ##STR80##           2H                                      3.10     (t)     OCHCS                1H                                      ______________________________________                                    

the IR analysis is as follows:

1365 cm⁻¹, 1380, 1460, 1700, 2880, 2940, 2960.

EXAMPLE V A. PREPARATION OF 1-CHLORO-1,3-DIPHENYL-2-PROPANONE Reaction:##STR81##

Into a 250 ml, three-necked flask equipped with 15 cm Vigreux columnwith vacuum outlet at top, pot thermometer, magnetic stirrer, 125 mladdition funnel and cold water bath is placed 99 grams (0.470 moles) of1,3-diphenylacetone. Over a period of 11/2 hours, 21.2 grams (0.157moles) of SO₂ Cl₂ is added while maintaining the reaction temperature inthe range of 23°-30° C., and with stirring. At the end of the additionof the SO₂ Cl₂, water aspirator vacuum is applied to remove the acidicgases, HCl and SO₂. An additional 21.2 grams of SO₂ Cl₂ is then addedover a 45 minute period, but allowing the reaction temperature to riseto a maximum of 38° C. (without cooling). The reaction mass is thenstirred for an additional hour while maintaining the temperature thereofat 24°-38° C. and acidic gases are again removed using water aspiratorvacuum, over a period of 2 hours. The reaction mass is then transferredto a 250 ml, three-necked, round bottom flask equipped with potthermometer, nitrogen inlet capillary tube, 1.8 × 30 cm distillationcolumn packed with 1/4 inches helices, reflux distillation head, vacuumpump and heating mantle. After 15 minutes of distillation, the packedcolumn was replaced with a 2.8 × 30 cm Vigreux column. Four cuts wereremoved at a vacuum of 0.2-0.5 mm Hg, and a vapor temperature of153°-163° C.

Thin layer chromatography was carried out on the fractions since the GLCanalysis cannot distinguish between the chlorinated derivative and thestarting material. TLC and mass spectral analyses yield the informationthat the distillate is a mixture of starting material and the desiredproduct, having the structure: ##STR82##

B. PREPARATION OF 1-PROPYLTHIO-1,3-DIPHENYL-2-PROPANONE Reaction:##STR83##

Into a 50 ml, three-necked, round bottom flask equipped with magneticstirrer, "Y" tube, reflux condenser, pot thermometer and nitrogen inlettube is placed a solution of 0.54 grams sodium methoxide dissolved in 6ml anhydrous methanol. The reaction mass is cooled and remains at 25° C.while a solution of 0.76 grams of n-propylmercaptan (0.01 moles)dissolved in 6 ml anhydrous methanol is added to the sodium methalatesolution. A solution of 2.5 grams of the mixture of1-chloro-1,3-diphenyl-2-propanone and 1,3-diphenyl-2-propanone dissolvedin 3 ml anhydrous methanol (prepared according to the procedure of PartA) is added to the reaction mass while allowing the reaction mass towarm to a temperature of 29° C.

The reaction mass is maintained at a temperature of between 25° and 39°C. over a period of 4 hours. At the end of the 4-hour period thereaction mixture is concentrated on a rotary evaporator using wateraspirator vacuum to a slurry which is an amber liquid and a white solid.Ten ml water are added to the mixture in order to dissolve the solid.The organic phase is then extracted with three 8 ml portions ofmethylene chloride, and the extracts are combined and washed with two 8ml portions of water. The combined extracts are dried over anhydroussodium sulfate, gravity filtered and concentrated on a rotary evaporatorusing water aspirator vacuum to yield an orange amber oil weighing 2.2grams. GLC analysis (8 feet × 1/4 inches SE-30 column) as well as massspectral, IR, NMR and thin layer chromatography (30% diethyl ether inhexane) analyses confirm that the desired product (isolated by GLCtrapping) is 1-propylthio-1,3-diphenyl-2-propanone having the structure:##STR84##

The NMR spectrum is set forth in FIG. 23. The IR spectrum is set forthin FIG. 24.

The mass spectral analysis is as follows:

    ______________________________________                                        m/e      Relative Intensity                                                   ______________________________________                                        43       8.sup.5                                                              65       7.sup.6                                                              91       47.sup.2                                                             118      6                                                                    123      20.sup.3                                                             165      100.sup.1                                                            166      14.sup.4                                                             167      5                                                                    210      5                                                                    M 284    9                                                                    ______________________________________                                    

The NMR analysis is as follows:

    ______________________________________                                        0.88 ppm (t)     CH.sub.3           3H                                        1.49     (m)     CH.sub.2           2H                                        2.34     (t)     CH.sub.2S          2H                                        3.76     (AB)                                                                                   ##STR85##         2H                                        4.68     (s)                                                                                    ##STR86##         1H                                        7.32-7.01                                                                              (m)     aromatic protons   10H                                       ______________________________________                                    

the IR analysis is as follows:

690 cm⁻¹, 1450, 1490, 1710, 2920, 2960, 3020.

Material prepared similarly to above example was vacuum distilledyielding 98.5% pure product (boiling boint 160°-163° C. at 0.4 mm Hg).The thus-distilled material has the same physical properties as setforth above for 1-propylthio-1,3-diphenyl-2-propanone.

EXAMPLE VI (A) PREPARATION OF 3-METHYLTHIO-2,6-DIMETHYL-4-HEPTANONE##STR87##

Into a 50 ml, three-necked, round bottom flask equipped with potthermometer, magnetic stirrer, gas inlet tube (subsurface), gas bubbler,methyl mercaptan gas cylinder, 15 ml Vigreux column, gas outlet tubeleading to stirred 10% sodium hydroxide solution, and cold water bath isadded a solution of 0.54 grams of sodium methoxide in 12 ml anhydrousmethanol (0.01 moles sodium methoxide). The reaction mass warms to 30°C., and it is cooled to 23° C. using the cold water bath. Over a periodof 20 minutes the methyl mercaptan is bubbled in below the surface ofthe liquid while maintaining the temperature of the reaction mass at22°-23° C. The reaction flask is then flushed with dry nitrogen, and asolution of 1.77 grams of 3-chloro-2,6-dimethyl-4heptanone dissolved in2 ml anhydrous methanol is then added to the reaction mass. The reactionmass remains at 23°-25° C. and is stirred at that temperature for aperiod of 2.5 hours. GLC analysis indicates 79% product. The reactionmass is then warmed to 35° C. and maintained at 28°-35° C. for another1.5 hours.

The reaction mass is then concentrated to a volume of 5 ml using arotary evaporator to which water aspirator vacuum is applied. 15 mldistilled water is then added to dissolve the solid yielding a two phasemixture (an aqueous phase and an organic phase). The reaction mass isthen extracted with three 10 ml portions of methylene chloride, and theextracts are combined and washed with 10 ml of water. The combinedextracts are then dired over anhydrous sodium sulfate, gravity filteredand concentrated on a rotary evaporator to a weight of 1.56 grams. GLC,MS/NMR and IR analyses yield the information that the resulting materialis 89.6% product, 3-methylthio-2,6-dimethyl-4-heptanone. The purematerial is trapped out using preparative GLC (conditions: 8 feet × 1/4inches SE-30 column).

The NMR spectrum is set forth in FIG. 25. The IR spectrum is set forthin FIG. 26.

The mass spectral analysis is as follows:

    ______________________________________                                        m/e      Relative Intensity                                                   ______________________________________                                        41       8.sup.5                                                              55       32.sup.2                                                             57       12.sup.3                                                             61       5                                                                    69       5                                                                    85       7.sup.6                                                              102      6                                                                    103      100.sup.1                                                            104      6                                                                    M 188    10.sup.4                                                             ______________________________________                                    

The NMR analysis is as follows:

    ______________________________________                                        0.94, 1.08 ppm                                                                             Methyl protons   12H                                             1.90         CH.sub.3S        3H                                              2.37 -  1.96 Methine protons  2H                                              2.49                                                                                        ##STR88##       2H                                              2.78                                                                                        ##STR89##       1H                                              ______________________________________                                    

the IR analysis is as follows:

1035 cm⁻¹, 1160, 1360, 1380, 1400, 1465, 1695, 2870, 2920, 2960

B. PREPARATION OF 3-METHYLTHIO-2,6-DIMETHYL-4-HEPTANOL Reaction:##STR90##

Into a 25 ml, three-necked, round bottom flask equipped with magneticstirrer, reflux condenser, pot thermometer, warm water bath, nitrogeninlet (to flush with dry nitrogen) is placed a solution of 0.10 grams(0.00265 moles) of sodium borohydride dissolved in 4 ml anhydrousethanol. Over a period of 1 minute with stirring at 23° C., a solutionof 0.9 grams of 3-thiomethyl-2,6-dimethyl-4-heptanone in 4 ml anhydrousethanol (prepared according to Part A) is added to the reaction mass.The reaction mass remains at 23° C. for a period of 1 hour, and then iswarmed to a temperature of 31° C. and maintained at 24-31° C. for aperiod of 25 hours, after which time 0.2 grams additional sodiumborohydride dissolved in 6 ml anhydrous ethanol is added. The reactionmass is continued to be stirred for a period of 3 hours at which time itis determined by GLC analysis (8feet × 1/4 inch SE-30 column) that thereaction mass contains 56.9% desired product. After adding another 0.15grams of sodium borohydride dissolved in 5 ml anhydrous ethanol withstirring, and stirring the reaction mass for a period of 4 hours at roomtemperature, it is determined that 73.4% desired product exists.

The reaction mass is then concentrated on a rotary evaporator (usingwater aspirator vacuum) to a 4 ml volume slurry. Six ml water is addedto the resulting slurry and the solid dissolves. The reaction mass nowexists in two phases; an aqueous phase and an organic phase. Thereaction mass is neutralized with 10% HCl solution to a pH of 5-6. Theoil is extracted with two 20 ml portions of methylene chloride. Theextracts are washed with water, dried over anhydrous sodium sulfate,gravity filtered and concentrated on a rotary evaporator to a weight of0.58 grams (pale yellow liquid). GLC, MS, NMR and IR analyses yield theinformation that the resultant product contains 79.1%3-methylthio-2,6-dimethyl-4-heptanol. The pure material is trapped outusing preparative GLC (conditions: 8 feet × 1/4 inch SE-30 column) andhas the structure: ##STR91##

The NMR spectrum is set forth in FIG. 27. The infrared spectrum is setforth in FIG. 28.

The mass spectral analysis is as follows:

    ______________________________________                                        m/e      Relative Intensity                                                   ______________________________________                                        43       21                                                                   55       55.sup.4                                                             56       25.sup.6                                                             57       35.sup.5                                                             61       19                                                                   69       21                                                                   89       68.sup.3                                                             103      100.sup.1                                                            104      77.sup.2                                                             M 190    19                                                                   ______________________________________                                    

The NMR analysis is as follows:

    ______________________________________                                        1.12 ppm - 0.90 methyl protons  12H                                           1.34            methine protons 2H                                            1.92            -- CH.sub.2 --  2H                                            2.16            CH.sub.3 -- S-- 3H                                            2.36            S-- HC-- C-- O--                                                                              1H                                            3.84            HC--O--         1H                                            ______________________________________                                    

The IR analysis is as follows:

1050 cm⁻¹, 1360, 1385, 1460, 2860, 2920, 2950, 3460.

EXAMPLE VII PREPARATION OF 3-METHOXY-4-HEPTANONE ##STR92##

A solution of 1.5 grams of 3-chloro-4-heptanone in 3 ml anhydrousmethanol (0.01 moles 3-chloro-4-heptanone) is placed into a 25 ml,three-necked, round bottom flask equipped with magnetic stirrer, potthermometer, reflux condenser (with drying tube), 10 ml addition funnelwith nitrogen inlet at top, an ice water-salt bath, and nitrogenbubbler. The 3-chloro-4-heptanone solution is cooled to a temperature ofbetween 0° and 1° C. Into the 10 ml addition funnel is placed a solutionof 0.54 grams of sodium methoxide dissolved in 7 ml anhydrous methanol(0.01 moles sodium methoxide). Over a period of one hour, whilemaintaining the reaction mass at a temperature of between 0° and 1° C.,the sodium methoxide solution is added to the 3-chloro-4-heptanone. Thereaction mass is then permitted to warm up to room temperature. It isthen vacuum filtered thereby separating the white precipitate from thefiltrate. The white solid precipitate is washed with 25 ml methylenechloride, and the washings are combined with the filtrate prior toconcentration. After concentration of the filtrate, the concentrate isdried over anhydrous sodium sulfate and further concentrated to a weightof 1.0 grams (white oil). The major peak is isolated by GLC trapping (8feet × 1/4 inch SE-30 column). NMR, IR and mass spectral analysesconfirm that the resulting material has the structure: ##STR93##

The NMR spectrum is set forth in FIG. 29. The IR spectrum is set forthin FIG. 30.

The NMR analysis is as follows:

    ______________________________________                                        0.95 ppm (t)     CH.sub.3           6H                                        1.64     (m)     CH.sub.2           4H                                        2.49     (t)                                                                                    ##STR94##         2H                                        3.36     (s)     CH.sub.3O          3H                                        3.54     (t)                                                                                    ##STR95##         1H                                        ______________________________________                                    

the infrared analysis is as follows:

1090 cm⁻¹, 1120, 1195, 1355, 1375, 1450, 1710, 2820, 2880, 2940, 2960.

EXAMPLE VIII RASPBERRY FLAVOR FORMULATION

The following basic raspberry flavor formulation is produced:

    ______________________________________                                        Ingredient              Parts by Weight                                       ______________________________________                                        Vanillin                2.0                                                   Maltol                  5.0                                                   Parahydroxybenzylacetone                                                                              5.0                                                   Alpha-ionone (10% in propylene glycol)                                                                2.0                                                   Ethyl Butyrate          6.0                                                   Ethyl Acetate           16.0                                                  Dimethyl Sulfide        1.0                                                   Isobutyl Acetate        13.0                                                  Acetic Acid             10.0                                                  Acetaldehyde            10.0                                                  Propylene Glycol        930.0                                                 ______________________________________                                    

3-methoxy-4-heptanone produced according to Example VII is added to halfof the above formulation at the rate of 0.2%. The formulation with the3-methoxy-4-heptanone produced according to Example VII is compared withthe formulation without the 3-methoxy-4-heptanone produced according toExample VII at the rate of 0.01 percent (100 ppm) in water and evaluatedby a bench panel.

The flavor containing the 3-methoxy-4-heptanone produced according toExample VII is found to have a substantially more pleasant and betterraspberry aroma. It is the unanimous opinion of the bench panel that thechemical, 3-methoxy-4-heptanone produced according to Example VII,rounds the flavor out and contributes to a very natural fresh aroma andtaste as found in full ripe raspberries. Accordingly, the flavor withthe addition of the 3-methoxy-4-heptanone produced according to ExampleVII is considered as substantially better than the flavor without the3-methoxy-4-heptanone produced according to Example VII. EXAMPLE IX

The following formulations are produced:

    ______________________________________                                        Formulation A                                                                 1.9 gm    Natural black current juice, concentrate                            0.1 gm    Natural black current esters                                        10.0 ml   Sugar Syrup 32° Be                                           q.s. 100 ml                                                                             Spring water                                                        Formulation B                                                                 1.9 gm    Natural black current juice, concentrate                            0.1 gm    Buchu leaf oil 0.1% (ethanol 95%)                                   10.0 ml   Sugar Syrup 32° Be                                           q.s. 100 ml                                                                             Spring water                                                        Formulation C                                                                 1.9 gm    Natural black current juice, concentrate                            0.1 gm    Niribine* 10% (ethanol 95%)                                         10.0 ml   Sugar Syrup 32° Be                                           q.s. 100 ml                                                                             Spring water                                                        Formulation D                                                                 1.9 gm    Natural black current juice, concentrate                            0.1 gm    3-methylthio-4-heptanone                                            10.0 ml   Sugar Syrup 32° Be                                           q.s. 100 ml                                                                             Spring water                                                        Formulation E                                                                 1.9 gm    Natural black current juice, concentrate                            10.0 ml   Sugar Syrup 32° Be                                           q.s. 100 ml                                                                             Spring Water                                                        ______________________________________                                         *Niribine is produced by distilling an alcoholic macerate of black curren     buds.                                                                    

Each of the above-mentioned formulations is compared with one another bya panel composed of 10 tasters. Formulation E is generally considered bythe panel to be flat and not very characteristic for fresh blackcurrant. Formulations B, C and D are considered as having substantiallyfresh and more pleasant notes than formulation E. In summary,formulation D is preferred as the best black currant juice formulation.In conclusion, for use in black currant flavor, the material3-methylthio-4-heptanone can be used at rates of one-tenth of that ofBuchu leaf oil in black currant juice.

It is further to be concluded that 3-methylthio-4-heptanone cansuccessfully replace Buchu leaf oil, Niribine and/or natural blackcurrant esters wherever the ingredient is used in reinforced blackcurrant juices, substituted black currant juices and imitation blackcurrant flavors.

EXAMPLE X BASIC BLACK CURRANT FORMULATION

3-(methallylthio)-2,6-dimethyl-4-heptanone produced according to ExampleII (C) has been added to a basic black currant flavor formulation at therate of 1.5%. Both flavors have been compared in water at the rate of200 ppm and evaluated by a bench panel. The flavor containing3-(methallylthio)-2,6-dimethyl-4-heptanone has had the characteristicaroma and taste of ripe black currants or fresh black currant juice.This typical note was not present in the basic black currantformulation. Therefore all members of the panel preferred the flavorcontaining 3-(methallylthio)-2,6-dimethyl-4-heptanone. Detailed below isthe Basic Black Currant Formulation to which is added3-(methallylthio)-2,6-dimethyl-4-heptanone at the rate of 1.5%.

    ______________________________________                                        Ingredient              Parts by Weight                                       ______________________________________                                        Cis-3-hexen-1-ol        5                                                     Alpha-phellandrene      1.5                                                   Terpineol-4 10% (in ethyl alcohol)                                                                    3                                                     Para-hydroxy benzyl acetone                                                                           5                                                     Vanillin                2                                                     Ethyl maltol            6                                                     Methyl benzoate         2                                                     Benzaldehyde            2                                                     Benzylpropionate        4                                                     Isobutylacetate         5                                                     Coriander oil           0.5                                                   Ethylbutyrate           8                                                     Dimethylsulfide         3                                                     Fusel oil               8                                                     Acetic acid             10                                                    Alpha-ionone 10% (in ethyl alcohol)                                                                   0.5                                                   Ethyl heptanoate        0.5                                                   Propylene glycol        934                                                                           1000                                                  ______________________________________                                    

EXAMPLE XI

A. 120 grams of the flavor composition of Example X is emulsified in asolution containing 300 gm gum acacia and 700 gm water. The emulsion isspray-dried with a Bowen Lab Model Drier utilizing 250 c.f.m. of airwith an inlet temperature of 500° F., an outlet temperature of 200° F.,and a wheel speed of 50,000 r.p.m.

B. The following mixture is prepared:

    ______________________________________                                        Ingredient              Parts by Weight                                       ______________________________________                                        Liquid flavor composition of                                                  Example X               25                                                    Propylene glycol        1                                                     Cab-O-Sil M-5 (Brand of Silica                                                                        3                                                     produced by the Cabot Corporation                                             of 125 High Street, Boston,                                                   Mass. 02110;                                                                  Physical properties:                                                           Surface area: 200 m.sup.2 /gm                                                 Nominal Particle size: 0.012 microns                                          Density: 2.3 lbs./cu.ft.)                                                    Ethyl cellulose         8                                                     ______________________________________                                    

The Cab-O-Sil and ethyl cellulose is dispersed in the liquid flavorcomposition of Example X with vigorous stirring, thereby resulting in aviscous liquid. 65 Parts by weight of the powder flavor composition ofPart A is then blended into said viscous liquid, with stirring, at 25°C. for a period of 30 minutes resulting in a dry, free flowing,sustained release flavor powder.

EXAMPLE XII CHEWING GUM

100 parts by weight of chicle are mixed with 4 parts by weight of theflavor prepared in accordance with Example XI. 300 Parts of sucrose and100 parts of corn syrup are added. Mixing is effected in a ribbonblender with jacketed side walls of the type manufactured by the BakerPerkins Co.

The resultant chewing gum blend is then manufactured into strips 1 inchin width and 0.1 inches in thickness. The strips are cut into lengths of3 inches each. On chewing, the chewing gum has a pleasant, long-lastingblack currant flavor.

EXAMPLE XIII CHEWABLE VITAMIN TABLETS

The flavor material produced according to Example XI is added to aChewable Vitamin Tablet Formulation at a rate of 5 gm/Kg which ChewableVitamin Tablet Formulation is prepared as follows:

In a Hobart Mixer, the following materials are blended to homogeneity:

    ______________________________________                                                                Gms/1000                                                                      tablets                                               ______________________________________                                        Vitamin C (ascorbic acid) as ascorbic acid-                                    sodium ascorbate mixture 1:1                                                                           70.0                                                Vitamin B.sub.1 (thiamine mononitrate) as                                      Rocoat thiamine mononitrate 331/3 %                                           (Hoffman La Roche)       4.0                                                 Vitamin B.sub.2 (riboflavin) as Rocoat riboflavin                              331/3 %                  5.0                                                 Vitamin B.sub.6 (pyridoxine hydrochloride) as                                  Rocoat pyridoxine hydrochloride 331/3 %                                                                4.0                                                 Niacinamide as Rocoat niacinamide 331/3 %                                                               33.0                                                Calcium pantothenate      11.5                                                Vitamin B.sub.12 (cyanocobalamin) as Merck                                     0.1% in gelatin          3.5                                                 Vitamin E (dl-alpha tocopheryl acetate) as                                     dry Vitamin E acetate 331/3 % Roche                                                                    6.6                                                 d-Biotin                  0.044                                               Certified lake color      5.0                                                 Flavor of Example XI      2.5                                                 Sweetener - sodium saccharin                                                                            1.0                                                 Magnesium stearate lubricant                                                                            10.0                                                Mannitol q.s. to make     500.0                                               ______________________________________                                    

Preliminary tablets are prepared by slugging with flat-faced punches andgrinding the slugs to 14 mesh. 13.5 g dry Vitamin A Acetate and 0.6 gVitamin D are then added as beadlets. The entire blend is thencompressed using concave punches at 0.5 g each.

Chewing of the resultant tablets yields a pleasant, long-lasting,consistently strong black currant flavor for a period of 12 minutes.

EXAMPLE XIV

0.5% 3-propylthio-4-heptanone is added to a commercial quality ofgrapefruit oil. The oils with and without this chemical are compared inwater at the rate of 10 ppm. The aroma and taste characteristics of themodified oil is considered as much more characteristic of grapefruitpeel than of the oil without this chemical. Therefore, a bench panelunanimously prefers the oil containing 3-propylthio-4-heptanone.

EXAMPLE XV

The following mixture is prepared:

    ______________________________________                                        Ingredients           Parts by Weight                                         ______________________________________                                        Methyl anthranilate   11.0                                                    Ethyl acetate         9.0                                                     Ethyl anthranilate    2.5                                                     Ethyl butyrate        2.0                                                     Ethyl methyl phenyl glycidate                                                                       1.5                                                     Cinnamic alcohol      0.3                                                     Cognac oil            0.1                                                     Ethyl alcohol         73.6                                                    ______________________________________                                    

The above mixture is judged to be an acceptable grape flavor whenevaluated in a sweetened and acidified aqueous tasting solution. 1.5Parts of 3-methylthio-4-heptanone is added to the above flavor and asignificant improvement in aroma and taste is noted. When this isevaluated in the afore-mentioned tasting solution, it is judged to havean improved grape character and grape fidelity. It contains more freshconcord grape character, true fruitiness with a nuance of wine. Inaddition, it is judged to be a more rounded and natural flavor, superiorto the product made without the addition of 3-methylthio-4-heptanone inboth aroma and taste.

Similar results obtained when using 2.5 parts of 3-methoxy-4-heptanoneprepared according to Example VII.

EXAMPLE XVI BASIC BLACKCURRANT FORMULATION

3-Acetylthio-4-heptanone has been added to a basic black currant flavorformulation at the rate of 1.5%. Both flavors have been compared inwater at the rate of 200 ppm and evaluated by a bench panel. The flavorcontaining 3-acetylthio-4-heptanone has had the characteristic aroma andtaste of ripe black currants or fresh black currant juice. This typicalnote was not present in the basic black currant formulation. Thereforeall members of the panel preferred the flavor containing3-acetylthio-4-heptanone. Detailed below is the Basic Black CurrantFormulation to which is added 3-acetylthio-4-heptanone at the rate of1.5%:

    ______________________________________                                        Ingredient              Parts by Weight                                       ______________________________________                                        Cis-3-hexen-1-ol        5                                                     Alpha-phellandrene      1.5                                                   Terpineol-4 10% (in ethyl alcohol)                                                                    3                                                     Para-hydroxy benzyl acetone                                                                           5                                                     Vanillin                2                                                     Ethyl maltol            6                                                     Methyl benzoate         2                                                     Benzaldehyde            2                                                     Benzylpropionate        4                                                     Isobutylacetate         5                                                     Coriander oil           0.5                                                   Ethylbutyrate           8                                                     Dimethylsulfide         3                                                     Fusel oil               8                                                     Acetic acid             10                                                    Alpha-ionone 10% (in ethyl alcohol)                                                                   0.5                                                   Ethyl heptanoate        0.5                                                   Propylene glycol        934                                                                           1000                                                  ______________________________________                                    

EXAMPLE XVII GRAPEFRUIT FLAVOR

The following formulation is prepared:

    ______________________________________                                        Ingredients              Parts by Weight                                      ______________________________________                                        Grapefruit oil           92                                                   Bergamot oil             2                                                    Citral                   3                                                    Amyl alcohol             1                                                    Ethyl acetate            1                                                    (1,3-diethylacetonyl) (1,3-diisopropylacetonyl)                               sulfide                  1                                                    ______________________________________                                    

When the above grapefruit formulation is added to water at the rate of1%, an excellent grapefruit drink is prepared. The (1,3-diethylacetonyl)(1,3-diisopropylacetonyl)sulfide gives a fruitier peeliness to theinstant formulation thereby rendering it more desirable. The effectrendered by the (1,3-diethylacetonyl) (1,3-diisopropylacetonyl)sulfidecan also be rendered by using 0.5 parts of 3-methylthio-4-heptanone or3-propylthio-4-heptanone or 3-(methallylthio)-2,6-dimethyl-4-heptanoneor 3-crotylthio-2,6-dimethyl-4-heptanone or3-allylthio-2,6-dimethyl-4-heptanone.

EXAMPLE XVIII

3-Propylthio-4-heptanol is added to a commercial instant tomato soup mix("Tomatancreme Suppe, C. H. Knorr, Heilbrown, West Germany) at the rateof 2 ppm (based on the weight of the soup as ready to eat, produced byadding 80 g. of the dry soup mix to 1,000 ml water and then bringing theresulting mixture to a boil). A second "control" is prepared which isidentical to the initial sample except for the absence of the3-propylthio-4-heptanol. A four member panel of flavorists compared thecontrol to the soup containing 3-propylthio-4-heptanol. All four membersof the panel indicated a strong preference for the tomato soupcontaining the 3-propylthio-4-heptanol. All four members of the panelindicated that the soup containing the 3-propylthio-4-heptanol includesa fresh tomato note which is not present in the soup prepared withoutusing the 3-propylthio-4-heptanol.

EXAMPLE XIX

1-Propylthio-1,3-diphenyl-2-propanone is dissolved in 95% ethanol toprovide a 2% solution, and is held at room temperature for 24 hours. Itis then diluted with water to 0.1% and this solution has an aroma offresh green onions.

Various water solutions are prepared, as shown in the following Table IIand evaluated for taste:

                  Table II                                                        ______________________________________                                        Concentration (ppm)                                                                            Evaluation                                                   ______________________________________                                        0.002            Green onion character; near                                                    threshold level                                             0.010            Fresh green onion taste                                      ______________________________________                                    

The material is added to a chicken broth to obtain a concentration of0.010 ppm, and it is found that the chicken taste is deepened and that alight onion aftertaste is added. Increasing the concentration to 0.030ppm adds an onion aroma, and the fresh onion taste is dominating.

Repetition of the foregoing with beef broth shows no significantdifference at 0.010 ppm; a slightly lachrymatory aroma and an improvedgeneral taste at 0.030 ppm; and a dominating onion note with the beefbroth changed to onion soup at 0.2 ppm.

It is judged that this flavor additive can replace all flavor areaswhere fresh onion is used, and it is interesting enough to be used aloneto develop onion soup flavor characteristic.

EXAMPLE XX

Three meat-loaf type products are prepared according to the followingformulation:

    ______________________________________                                        Ingredient           Amount                                                   ______________________________________                                        TVP, minced          1 cup                                                    Ground beef          1 cup                                                    Water                1 cup                                                    Beef suet            1/3 cup                                                  Bread crumbs, dry, unflavored                                                                      1 cup                                                    Whole milk           1 cup                                                    Egg albumen          3 tbsp.                                                  Salt                 11/4 tbsp.                                               Black pepper         1/4 tsp.                                                 Catsup               1/4 cup                                                  Water                32 ml.                                                   ______________________________________                                    

The "TVP" is a texturized vegetable protein mixture made byArcher-Daniels-Midland Company.

Three separate portions prepared according to the foregoing formulationare made into three meat loaves. Loaf A contains no additional additive,Load B contains 32 ml of fresh pressed onion juice to replace the 32 mlof water, and Loaf C contains 0.6 ppm of1-propylthio-1,3-diphenyl-2-propanone.

The three loaves are baked at 350° F. for 1 hour and evaluated forflavor by a panel of twelve judges. The consensus of the judges is thatLoaves B and C are superior to Loaf A because the onion character of Band C enhances the overall taste and covers the dry, cardboard-likecereal character of Loaf A. It is accordingly apparent that the productof this invention is a valuable ingredient for a wide variety of flavorsand types of foodstuffs.

EXAMPLE XXI

A white bread dough mix is prepared by mixing 1350 g wheat flour and 800ml water. To the mix is added:

    ______________________________________                                        Ingredient              Amount (grams)                                        ______________________________________                                        Yeast                   27.0                                                  Sodium chloride         27.0                                                  Sucrose                 67.5                                                  Shortening              54                                                    Non-fat dry milk powder 40.5                                                  Yeast food (Arkady; Manufactured                                               by Fleischmann, Div. of                                                       Standard Brands)       0.50                                                  Softening agent (succinylated                                                  monoglycerides; Manufactured                                                  by Kraft Div. of National                                                     Dairy Products Corporation)                                                                          3.4                                                   ______________________________________                                    

The dough is then mixed for 8 minutes,3-[(methoxycarbonyl)methylthio]-4-heptanone (8 grams) is then mixed withthe resulting product for a period of 8 minutes. The dough is thenallowed to rise for 45 minutes at 40° C. The dough is then baked for 45minutes at 210° C.

The breadstuff product obtained has a flavor note reminiscent of thecrust of home made Italian bread and has acceptable and persistentflavor properties for a period of one week and has good flavorcharacteristics when spread with margarine.

By way of comparison, breadstuffs similarly prepared by omitting thesulfur-free amino acid-cyclic ketone reaction product and the3-[(methoxycarbonyl)methylthio]-4-heptanone have a flat taste, showtypical flavor deterioration on storage during a period of one week andrequire an expensive butter spread to provide an acceptable flavor.

BRIEF DESCRIPTION OF THE DRAWINGS:

FIG. 1 is the NMR spectrum for the product of Example I(B) wherein3-thioacetyl-4-heptanone is produced.

FIG. 2 is the IR spectrum for the product of Example I(B) wherein3-thioacetyl-4-heptanone is produced.

FIG. 3 is the NMR spectrum for the product of Example I(C) wherein3-thiomethyl-4-heptanone is produced.

FIG. 4 is the IR spectrum for the product of Example I(C) wherein3-thiomethyl-4-heptanone is produced.

FIG. 5 is the NMR spectrum for the product of Example I(D) wherein3-thiomethyl-4-heptanol is produced.

FIG. 6 is the IR spectrum for the product of Example I(D) wherein3-thiomethyl-4-heptanol is produced.

FIG. 7 is the NMR spectrum for the product of Example II(C) wherein3-methallylthio-2,6-dimethyl-4-heptanone is produced.

FIG. 8 is the IR spectrum for the product of Example II(C) wherein3-methallylthio-2,6-dimethyl-4-heptanone is produced.

FIG. 9 is the NMR spectrum for the product of Example II(D) wherein3-crotylthio-2,6-dimethyl-4-heptanone is produced.

FIG. 10 is the IR spectrum for the product of Example II(D) wherein3-crotylthio-2,6-dimethyl-4-heptanone is produced.

FIG. 11 is the NMR spectrum for the product of Example II(E) wherein3-allylthio-2,6-dimethyl-4-heptanone is produced.

FIG. 12 is the IR spectrum for the product of Example II(E) wherein3-allylthio-2,6-dimethyl-4-heptanone is produced.

FIG. 13 is the NMR spectrum for the product of Example II(F) wherein(1,3-diethylacetonyl) (1,3-diisopropylacetonyl) sulfide is produced.

FIG. 14 is the IR spectrum for the product of Example II(F) wherein(1,3-diethylacetonyl) (1,3-diisoproylacetonyl) sulfide is produced.

FIG. 14(A) is the NMR spectrum for the product of Example II(G) wherein3-[(methoxycarbonyl)methylthio]-2,6-dimethyl-4-heptanone is produced.

FIG. 14(B) is the IR spectrum for the product of Example II(B) wherein3-[(methoxycarbonyl)methylthio]-2,6-dimethyl-4-heptanone is produced.

FIG. 15 is the NMR spectrum for the product of Example II(H) wherein3-[(methoxycarbonyl)methylthio]-4-heptanone is produced.

FIG. 16 is the IR spectrum for the product of Example II(H) wherein3-[(methoxycarbonyl)methylthio]-4-heptanone is produced.

FIG. 17 is the NMR spectrum for the product of Example III(A) wherein3-n-propylthio-4-heptanone is produced.

FIG. 18 is the IR spectrum for the product of Example III(A) wherein3-n-propylthio-4-heptanone is produced.

FIG. 19 is the NMR spectrum for the product of Example III(A) wherein3-n-propylthio-4-heptanol is produced.

FIG. 20 is the IR spectrum for the product of Example III(A) wherein3-n-propylthio-4-heptanol is produced.

FIG. 21 is the NMR spectrum for the product of Example IV wherein3-isobutylthio-4-heptanone is produced.

FIG. 22 is the IR spectrum for the product of Example IV wherein3-isobutylthio-4-heptanone is produced.

FIG. 23 is the NMR spectrum for the product of Example V(B) wherein1-propylthio-1,3-diphenyl-2-propanone is produced.

FIG. 24 is the IR spectrum for the product of Example V(B) wherein1-propylthio-1,3-diphenyl-2-propanone is produced.

FIG. 25 is the NMR spectrum for the product of Example VI(A) wherein3-methylthio-2,6-dimethyl-4-heptanone is produced.

FIG. 26 is the IR spectrum for the product of Example VI(A) wherein3-methylthio-2,6-dimethyl-4-heptanone is produced.

FIG. 27 is the NMR spectrum for the product of Example VI(B) wherein3-methylthio-2,6-dimethyl-4-heptanol is produced.

FIG. 28 is the IR spectrum for the product of Example VI(B) wherein3-methylthio-2,6-dimethyl-4-heptanol is produced.

FIG. 29 is the NMR spectrum for the product of Example VII wherein3-methoxy-4-heptanone is produced.

FIG. 30 is the IR spectrum for the product of Example VII wherein3-methoxy-4-heptanone is produced.

What is claimed is:
 1. A process for augmenting or enhancing the tasteor aroma of a foodstuff comprising the step of adding to said foodstufffrom about 0.1 ppm up to about 50 ppm by weight of said foodstuff of analpha oxosulfide compound having the structure: ##STR96##
 2. A flavoraugmenting or enhancing composition comprising from about 0.1% up toabout 15% by weight based on total weight of said flavoring compositionof an alpha oxosulfide compound having the structure: ##STR97## and theremainder of said composition being at least one adjuvant for said alphaoxosulfide compound selected from the group consistingof:p-Hydroxybenzyl acetone; Geraniol; Acetaldehyde; Maltol; Ethyl methylphenyl glycidate; Benzyl acetate; Dimethyl sulfide; Vanillin; Methylcinnamate; Ethyl pelargonate; Methyl anthranilate; Isoamyl acetate;Isobutyl acetate; Alpha ionone; Ethyl butyrate; Acetic acid;Gamma-undecalactone; Naphthyl ethyl ether; Diacetyl; Ethyl acetate;Anethole; Isoamyl butyrate; Cis-3-hexenol-1; 2-Methyl-2-pentenoic acid;4-allyl-1,2,6-trimethoxy benzene; 4-propenyl-1,2,6-trimethoxy benzene;2-(4-hydroxy-4-methylpentyl) norbornadiene; Natural blackcurrant juiceBuchu leaf oil; α-phellandrene; Cis-3-hexen-1-ol; Terpinenol-4; Ethylmaltol; Methyl benzoate; Benzaldehyde; Coriander oil; α-ionone; Ethylheptanoate; Ethyl anthranilate; Cinnamic alcohol; Amyl valerianate;Cinnamyl propionate; Rhodinyl acetate; Methyl β-hydroxy butyrate; Ethylβ-hydroxy butyrate; 2-phenyl-3-carboethoxyfuran; Cyclohexyl disulfide;Grapefruit oil; Nootkatone; Bergamot oil; Citral; Amyl alcohol;5-phenyl-4-pentenal; 5-phenyl-2-pentenal; Allyl caproate; 2-(n-pentyl)thiazole; 2-(i-butyl) thiazole; 2-(i-propyl) thiazole; 2-(n-propyl)thiazole; 2-phenyl-4-pentenal; 2-phenyl-4-pentenaldimethylacetal;Methional; 4-methylthiobutanal; 2-ethyl-3-acetylpyrazine, Tetramethylpyrazine; 2-methyl pyrazine; trans-2-hexenal; Hydrolyzed vegetableprotein; Monosodium glutamate; Dimethyl disulfide; Methyl propyldisulfide; Methyl propenyl disulfide; Methyl allyl disulfide; Allylpropyl disulfide; Propyl propenyl disulfide; Dipropyl disulfide; Diallyldisulfide; Propyl propenyl trisulfide; Thiopropanal-S-oxide;Thiobutanal-S-oxide; Thioethanal-S-oxide; Thiohexanal-S-oxide; andPropyl propene thiosulfonate.